CN114854093A - Carbon black applied to modified pyrolysis and preparation process thereof - Google Patents
Carbon black applied to modified pyrolysis and preparation process thereof Download PDFInfo
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- 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
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/02—Elements
- C08K3/04—Carbon
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K9/00—Use of pretreated ingredients
- C08K9/02—Ingredients treated with inorganic substances
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K9/00—Use of pretreated ingredients
- C08K9/04—Ingredients treated with organic substances
- C08K9/06—Ingredients treated with organic substances with silicon-containing compounds
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
- Y02W30/50—Reuse, recycling or recovery technologies
- Y02W30/62—Plastics recycling; Rubber recycling
Abstract
The invention discloses modified pyrolysis carbon black and a preparation process thereof, relating to the technical field of pyrolysis carbon black production and comprising the following raw materials in parts by weight: the modified cracking carbon black is applied to the modified cracking carbon black and a preparation process thereof, the cracking carbon black is modified, the dispersibility of the cracking carbon black in rubber is improved, the addition amount of the cracking carbon black in rubber can be further improved, and the addition of the modifier, the oxidant and the silane coupling agent improves the purity of the carbon black, so that the carbon black is directly contacted with the rubber, and the dispersing performance of the modified cracking carbon black in the rubber is ensured; the preparation process adopts direct granulation after drying, so that the preparation process is simple, the process production is convenient, and the modified pyrolysis carbon black has excellent performance in production.
Description
Technical Field
The invention relates to the technical field of production of pyrolysis carbon black, in particular to modified pyrolysis carbon black and a preparation process thereof.
Background
The cracking carbon black (CBp for short) is one of the important products of waste tire thermal cracking, the surface ash content and carbonaceous sediment content of the cracking carbon black are high, the surface activity is poor, the particle size is large, the structure degree is low, the untreated cracking carbon black can only be used as a low-end rubber product, the functionality and the economic benefit are not ideal, the tire is a circular ring-shaped elastic rubber product which is assembled on various vehicles or machines and rolls with the ground, the cracking carbon black is mostly obtained from waste rubber tires, and the cyclic utilization of resources is realized.
The pyrolysis carbon black in the prior art has poor reinforcing effect on rubber due to high content of surface ash and carbonaceous sediments, uneven particle size, low structure degree and poor surface activity, and the existing carbon black modification methods comprise ash removal treatment, plasma modification, supercritical modification, ultrafine grinding modification and the like, but the treatment methods have the problems of large waste liquid amount, serious environmental pollution, large equipment investment, unstable modification effect, complicated modification process and the like, and the efficient and reasonable utilization of the pyrolysis carbon black is difficult to realize.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides a modified pyrolysis carbon black and a preparation process thereof, which are used for solving the problems in the background art.
In order to achieve the purpose, the invention provides the following technical scheme: the carbon black applied to modified pyrolysis is characterized by comprising the following raw materials in parts by weight: 65-70 parts of cracking carbon black, 1-3 parts of carbon black dispersing agent, 1-2 parts of modifying agent, 1-3 parts of stearic acid, 15-20 parts of oxidizing agent, 4-6 parts of aromatic oil, 2-4 parts of protective wax, 2-4 parts of silane coupling agent and 2-5 parts of treating agent.
1. The process of claim 1, comprising the steps of:
s1, preparation of cracking carbon black powder: crushing waste tire pyrolysis carbon black, and screening powder with a certain particle size distribution range to obtain pyrolysis carbon black powder;
s2, preparation of carbon black slurry: putting the cracking carbon black powder prepared in the step S1 into a stirrer, adding a carbon black dispersing agent into the stirrer, and mixing to obtain the required carbon black slurry;
s3, preparation of a mixed solution I: adding a modifier, stearic acid, zinc oxide and protective wax into the carbon black slurry prepared in the step S2, and uniformly stirring to obtain a required mixed solution I for later use;
s4, preparing a mixed solution II: sequentially adding aromatic oil, a silane coupling agent and an oxidant into the mixed solution in the step S3, and uniformly mixing to obtain a required mixed solution II for later use;
s5, aging and modifying: adding an oxidant into the mixed solution II in the step S4, and performing aging modification operation after uniformly mixing;
s6, preparation of a modified liquid: filtering the mixed solution aged and modified in the step S5 to obtain a required modified solution;
s7, preparation of a dehydrated solid: heating the modified liquid prepared in the step S6 to 90-95 ℃, preserving heat for 1h, adding a treating agent, and uniformly stirring to obtain a dehydrated paste;
s8, drying the dehydrated paste prepared in the step S7, and granulating to obtain the required modified pyrolysis carbon black.
Further optimizing the technical scheme, the particle size of the cracking carbon black powder in the step S1 is 10-15 μm.
Further optimizing the technical scheme, the modifier in the step S3 is NaOH aqueous solution.
Further optimizing the technical scheme, the silane coupling agent in the step S4 is Si 69; the time for aging modification in the step S5 is 50-70 min.
Further optimizing the technical scheme, the dehydrated paste in the step S8 is subjected to microwave heating treatment under the sweeping of inert gas, the heating temperature is 200-225 ℃, and the heating time is 1.5-2 h.
Further optimizing the technical scheme, the oxidant in the step S4 is one of hydrogen peroxide, nitric acid, ozone or sulfuric acid, and the oxidation reaction time of the oxidant is 0.5-12 h.
Further optimizing the technical scheme, the steps S2, S3 and S4 all adopt mechanical stirring and ultrasonic treatment, the rotation speed of the mechanical stirring is 200-800r/m, the power of the ultrasonic treatment is 100-200w, the reaction time is 2-6h, the reaction temperature is 40-90 ℃, and the standing time after the reaction is finished is 6-10 h.
Further optimizing the technical scheme, the treating agent in the step S7 is prepared from 80-90 parts by weight of carbon fiber and 10-20 parts by weight of hydroxylated modifier.
Compared with the prior art, the invention provides the modified pyrolysis carbon black and the preparation process thereof, and the modified pyrolysis carbon black has the following beneficial effects:
1. according to the modified pyrolysis carbon black and the preparation process thereof, the pyrolysis carbon black is modified, so that the dispersibility of the pyrolysis carbon black in rubber is improved, the addition amount of the pyrolysis carbon black in rubber can be further improved, the addition of a modifier, an oxidant and a silane coupling agent is improved, the purity of the carbon black is improved, the carbon black is directly contacted with the rubber, and the dispersibility of the modified pyrolysis carbon black in the rubber is ensured.
2. The preparation process adopts direct granulation after drying, so that the preparation process is simple, thereby facilitating the industrialized production and ensuring that the modified pyrolysis carbon black has excellent performance in production.
Drawings
FIG. 1 is a schematic flow chart of a modified pyrolysis carbon black and a preparation process thereof according to the present invention.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The first embodiment is as follows: referring to fig. 1, the invention discloses a modified pyrolysis carbon black, which comprises the following raw materials in parts by weight: 65 parts of cracking carbon black, 2 parts of carbon black dispersing agent, 2 parts of modifying agent, 2 parts of stearic acid, 18 parts of oxidizing agent, 5 parts of aromatic oil, 3 parts of protective wax, 3 parts of silane coupling agent and 3 parts of treating agent.
A preparation process applied to modified pyrolysis carbon black comprises the following steps:
s1, preparation of cracking carbon black powder: crushing the waste tire pyrolysis carbon black, and screening powder with a certain particle size distribution range to obtain pyrolysis carbon black powder, wherein the particle size of the pyrolysis carbon black powder is 10-15 mu m;
s2, preparation of carbon black slurry: putting the cracking carbon black powder prepared in the step S1 into a stirrer, adding a carbon black dispersing agent into the stirrer, and mixing to obtain the required carbon black slurry;
s3, preparation of a mixed solution I: adding a modifier, stearic acid, zinc oxide and protective wax into the carbon black slurry prepared in the step S2, wherein the modifier is NaOH aqueous solution, and uniformly stirring to obtain a required mixed solution I for later use;
s4, preparing a mixed solution II: sequentially adding aromatic oil, a silane coupling agent and an oxidant into the mixed solution in the step S3, wherein the silane coupling agent is Si69, the aging modification time is 60min, the required mixed solution II is obtained after uniform mixing, the oxidant is one of hydrogen peroxide, nitric acid, ozone or sulfuric acid, the oxidation reaction time of the oxidant is 3h, the preparation of S2, S3 and S4 adopts mechanical stirring and ultrasonic treatment, the rotating speed of the mechanical stirring is 200-800r/m, the power of the ultrasonic treatment is 150w, the reaction time is 2-6h, the reaction temperature is 60 ℃, and the standing time is 6-10h after the reaction is finished for later use;
s5, aging and modifying: adding an oxidant into the mixed solution II in the step S4, and performing aging modification operation after uniformly mixing;
s6, preparation of a modified liquid: filtering the mixed solution aged and modified in the step S5 to obtain a required modified solution;
s7, preparation of a dehydrated solid: heating the modified liquid prepared in the step S6 to 95 ℃, preserving heat for 1h, adding a treating agent, wherein the treating agent is prepared from 80 parts by weight of carbon fiber and 15 parts by weight of hydroxylation modifying agent, and uniformly stirring to obtain a dehydrated paste;
s8, drying the dehydrated paste prepared in the step S7, granulating, and carrying out microwave heating treatment on the dehydrated paste under the sweeping of inert gas, wherein the heating temperature is 215 ℃, and the heating time is 1.8h, so that the required modified pyrolysis carbon black is obtained.
Example two: referring to fig. 1, the invention discloses a modified pyrolysis carbon black, which comprises the following raw materials in parts by weight: 70 parts of cracking carbon black, 2 parts of carbon black dispersing agent, 2 parts of modifier, 2 parts of stearic acid, 15-20 parts of oxidant, 5 parts of aromatic oil, 3 parts of protective wax, 3 parts of silane coupling agent and 3 parts of treating agent.
A preparation process applied to modified pyrolysis carbon black comprises the following steps:
s1, preparation of cracking carbon black powder: crushing the waste tire pyrolysis carbon black, and screening powder with a certain particle size distribution range to obtain pyrolysis carbon black powder, wherein the particle size of the pyrolysis carbon black powder is 13 mu m;
s2, preparation of carbon black slurry: putting the cracking carbon black powder prepared in the step S1 into a stirrer, adding a carbon black dispersing agent into the stirrer, and mixing to obtain the required carbon black slurry;
s3, preparation of a mixed solution I: adding a modifier, stearic acid, zinc oxide and protective wax into the carbon black slurry prepared in the step S2, wherein the modifier is NaOH aqueous solution, and uniformly stirring to obtain a required mixed solution I for later use;
s4, preparing a mixed solution II: sequentially adding aromatic oil, a silane coupling agent and an oxidant into the mixed solution obtained in the step S3, wherein the silane coupling agent is Si69, the aging modification time is 60min, the required mixed solution II is obtained after uniform mixing, the oxidant is one of hydrogen peroxide, nitric acid, ozone or sulfuric acid, the oxidation reaction time of the oxidant is 10h, the preparation of S2, S3 and S4 adopts mechanical stirring and ultrasonic treatment, the rotating speed of the mechanical stirring is 700r/m, the power of the ultrasonic treatment is 150w, the reaction time is 5h, the reaction temperature is 80 ℃, and the standing time is 8h after the reaction is finished for later use;
s5, aging and modifying: adding an oxidant into the mixed solution II in the step S4, and performing aging modification operation after uniformly mixing;
s6, preparation of a modified liquid: filtering the mixed solution aged and modified in the step S5 to obtain a required modified solution;
s7, preparation of a dehydrated solid: heating the modified solution prepared in the step S6 to 95 ℃, preserving heat for 1h, adding a treating agent, wherein the treating agent is prepared from 85 parts by weight of carbon fiber and 15 parts by weight of hydroxylation modifying agent, and uniformly stirring to obtain a dehydrated paste;
s8, drying the dehydrated paste prepared in the step S7, granulating, and carrying out microwave heating treatment on the dehydrated paste under the sweeping of inert gas, wherein the heating temperature is 215 ℃, and the heating time is 1.8h, so that the required modified pyrolysis carbon black is obtained.
Example three: referring to fig. 1, the invention discloses a modified pyrolysis carbon black, which comprises the following raw materials in parts by weight: 65 parts of cracking carbon black, 2 parts of carbon black dispersing agent, 1 part of modifying agent, 2 parts of stearic acid, 15-20 parts of oxidizing agent, 5 parts of aromatic oil, 3 parts of protective wax, 2 parts of silane coupling agent and 3 parts of treating agent.
A preparation process applied to modified pyrolysis carbon black comprises the following steps:
s1, preparation of cracking carbon black powder: crushing the waste tire pyrolysis carbon black, and screening powder with a certain particle size distribution range to obtain pyrolysis carbon black powder, wherein the particle size of the pyrolysis carbon black powder is 12 microns;
s2, preparation of carbon black slurry: putting the cracking carbon black powder prepared in the step S1 into a stirrer, adding a carbon black dispersing agent into the stirrer, and mixing to obtain the required carbon black slurry;
s3, preparation of a mixed solution I: adding a modifier, stearic acid, zinc oxide and protective wax into the carbon black slurry prepared in the step S2, wherein the modifier is NaOH aqueous solution, and uniformly stirring to obtain a required mixed solution I for later use;
s4, preparing a mixed solution II: sequentially adding aromatic oil, a silane coupling agent and an oxidant into the mixed solution obtained in the step S3, wherein the silane coupling agent is Si69, the aging modification time is 55min, the required mixed solution II is obtained after uniform mixing, the oxidant is nitric acid, the oxidation reaction time of the oxidant is 5h, the preparation of S2, S3 and S4 adopts mechanical stirring and ultrasonic treatment, the rotating speed of the mechanical stirring is 500r/m, the power of the ultrasonic treatment is 120w, the reaction time is 4h, the reaction temperature is 80 ℃, and the standing time is 8h after the reaction is finished for later use;
s5, aging and modifying: adding an oxidant into the mixed solution II in the step S4, and performing aging modification operation after uniformly mixing;
s6, preparation of a modified liquid: filtering the mixed solution aged and modified in the step S5 to obtain a required modified solution;
s7, preparation of a dehydrated solid: heating the modified solution prepared in the step S6 to 90 ℃, preserving heat for 1h, adding a treating agent, wherein the treating agent is prepared from 80 parts by weight of carbon fiber and 10 parts by weight of hydroxylation modifying agent, and uniformly stirring to obtain a dehydrated paste;
s8, drying the dehydrated paste prepared in the step S7, granulating, and carrying out microwave heating treatment on the dehydrated paste under the sweeping of inert gas, wherein the heating temperature is 215 ℃, and the heating time is 1.8h, so that the required modified pyrolysis carbon black is obtained.
Example four: referring to fig. 1, the invention discloses a modified pyrolysis carbon black, which comprises the following raw materials in parts by weight: 70 parts of cracking carbon black, 2 parts of carbon black dispersing agent, 1 part of modifying agent, 2 parts of stearic acid, 17 parts of oxidizing agent, 5 parts of aromatic oil, 3 parts of protective wax, 2 parts of silane coupling agent and 3 parts of treating agent.
A preparation process applied to modified pyrolysis carbon black comprises the following steps:
s1, preparation of cracking carbon black powder: crushing the waste tire pyrolysis carbon black, and screening powder with a certain particle size distribution range to obtain pyrolysis carbon black powder, wherein the particle size of the pyrolysis carbon black powder is 12 microns;
s2, preparation of carbon black slurry: putting the cracking carbon black powder prepared in the step S1 into a stirrer, adding a carbon black dispersing agent into the stirrer, and mixing to obtain the required carbon black slurry;
s3, preparation of a mixed solution I: adding a modifier, stearic acid, zinc oxide and protective wax into the carbon black slurry prepared in the step S2, wherein the modifier is NaOH aqueous solution, and uniformly stirring to obtain a required mixed solution I for later use;
s4, preparing a mixed solution II: sequentially adding aromatic oil, a silane coupling agent and an oxidant into the mixed solution obtained in the step S3, wherein the silane coupling agent is Si69, the aging modification time is 60min, the required mixed solution II is obtained after uniform mixing, the oxidant is hydrogen peroxide, the oxidation reaction time of the oxidant is 5h, the preparation of S2, S3 and S4 adopts mechanical stirring and ultrasonic treatment, the rotating speed of the mechanical stirring is 600r/m, the power of the ultrasonic treatment is 150w, the reaction time is 4h, the reaction temperature is 80 ℃, and the standing time is 7h after the reaction is finished for later use;
s5, aging and modifying: adding an oxidant into the mixed solution II in the step S4, and performing aging modification operation after uniformly mixing;
s6, preparation of a modified liquid: filtering the mixed solution aged and modified in the step S5 to obtain a required modified solution;
s7, preparation of a dehydrated solid: heating the modified liquid prepared in the step S6 to 90-95 ℃, preserving heat for 1h, adding a treating agent, wherein the treating agent is prepared from 80-90 parts by weight of carbon fiber and 10-20 parts by weight of hydroxylation modifying agent, and uniformly stirring to obtain a dehydrated paste;
s8, drying the dehydrated paste prepared in the step S7, granulating, and carrying out microwave heating treatment on the dehydrated paste under the sweeping of inert gas, wherein the heating temperature is 210 ℃, and the heating time is 1.5h, so that the required modified pyrolysis carbon black is obtained.
And (4) judging the standard: the modified pyrolysis carbon blacks prepared in the first to fourth examples and the comparative example were subjected to the performance test, and the results are shown in table 1:
| detecting items | Tensile Strength (MPa) | Elongation at Break (%) | Tear Strength (KN/m) | Degree of dispersion of carbon black | 200% definite elongation force (MPa) |
| Example one | 18.2 | 485 | 118 | 2.6 | 9.1 |
| Example two | 21.2 | 511 | 121 | 3.1 | 9.2 |
| EXAMPLE III | 21.3 | 532 | 125 | 3.23 | 9.5 |
| Example four | 20.8 | 522 | 123 | 2.9 | 9.15 |
| Comparative example (commercially available) | 17.8 | 475 | 115 | 2.5 | 8.9 |
Table 1 performance test results from the test data in the table above, it can be seen that the modified pyrolytic carbon black prepared by the present invention has a wide application prospect, and the best result is the third embodiment by comparing the four embodiments, so that the selection of the third embodiment as the best embodiment, the specific change of the amount also belongs to the protection scope of the technical scheme.
The invention has the beneficial effects that: according to the modified pyrolysis carbon black and the preparation process thereof, the pyrolysis carbon black is modified, so that the dispersibility of the pyrolysis carbon black in rubber is improved, the addition amount of the pyrolysis carbon black in rubber can be further improved, and the addition of a modifier, an oxidant and a silane coupling agent improves the purity of the carbon black, so that the carbon black is directly contacted with the rubber, and the dispersibility of the modified pyrolysis carbon black in the rubber is ensured; the preparation process adopts direct granulation after drying, so that the preparation process is simple, the process production is convenient, and the modified pyrolysis carbon black has excellent performance in production.
Although embodiments of the present invention have been shown and described, it will be appreciated by those skilled in the art that changes, modifications, substitutions and alterations can be made in these embodiments without departing from the principles and spirit of the invention, the scope of which is defined in the appended claims and their equivalents.
Claims (9)
1. The carbon black applied to modified pyrolysis is characterized by comprising the following raw materials in parts by weight: 65-70 parts of cracking carbon black, 1-3 parts of carbon black dispersing agent, 1-2 parts of modifying agent, 1-3 parts of stearic acid, 15-20 parts of oxidizing agent, 4-6 parts of aromatic oil, 2-4 parts of protective wax, 2-4 parts of silane coupling agent and 2-5 parts of treating agent.
2. The process of claim 1, comprising the steps of:
s1, preparation of cracking carbon black powder: crushing the waste tire pyrolysis carbon black, and screening powder with a certain particle size distribution range to obtain pyrolysis carbon black powder;
s2, preparation of carbon black slurry: putting the cracking carbon black powder prepared in the step S1 into a stirrer, adding a carbon black dispersing agent into the stirrer, and mixing to obtain the required carbon black slurry;
s3, preparation of a mixed solution I: adding a modifier, stearic acid, zinc oxide and protective wax into the carbon black slurry prepared in the step S2, and uniformly stirring to obtain a required mixed solution I for later use;
s4, preparing a mixed solution II: sequentially adding aromatic oil, a silane coupling agent and an oxidant into the mixed solution obtained in the step S3, and uniformly mixing to obtain a required mixed solution II for later use;
s5, aging and modifying: adding an oxidant into the mixed solution II in the step S4, and performing aging modification operation after uniformly mixing;
s6, preparation of a modified liquid: filtering the mixed solution aged and modified in the step S5 to obtain a required modified solution;
s7, preparation of a dehydrated solid: heating the modified liquid prepared in the step S6 to 90-95 ℃, preserving heat for 1h, adding a treating agent, and uniformly stirring to obtain a dehydrated paste;
s8, drying and granulating: and (5) drying the dehydrated paste prepared in the step S7, and granulating to obtain the required modified pyrolysis carbon black.
3. The process of claim 2, wherein the particle size of the pyrolysis carbon black powder in the step S1 is 10-15 μm.
4. The process of claim 2, wherein the modifying agent in step S3 is NaOH aqueous solution.
5. The process of claim 2, wherein the silane coupling agent in step S4 is Si 69; the time for aging modification in the step S5 is 50-70 min.
6. The process as claimed in claim 2, wherein the dehydrated paste obtained in step S8 is subjected to microwave heating under inert gas purge at 200-225 ℃ for 1.5-2 h.
7. The process of claim 2, wherein in step S4, the oxidant is one of hydrogen peroxide, nitric acid, ozone or sulfuric acid, and the oxidation reaction time of the oxidant is 0.5-12 h.
8. The process as claimed in claim 2, wherein the steps S2, S3 and S4 are performed by mechanical stirring and ultrasonic treatment, the rotation speed of the mechanical stirring is 200-800r/m, the power of the ultrasonic treatment is 100-200w, the reaction time is 2-6h, the reaction temperature is 40-90 ℃, and the standing time after the reaction is finished is 6-10 h.
9. The process of claim 2, wherein the treating agent in step S7 is 80-90 parts by weight of carbon fiber and 10-20 parts by weight of hydroxylated modifier.
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| CN115725122A (en) * | 2023-01-05 | 2023-03-03 | 浙江工业大学 | Carbon black rubber composite material and preparation method thereof |
| CN115725122B (en) * | 2023-01-05 | 2024-04-19 | 浙江工业大学 | Carbon black rubber composite material and preparation method thereof |
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| CN113372617A (en) * | 2021-07-01 | 2021-09-10 | 青岛科技大学 | Modification method and application of pyrolysis carbon black |
| CN113861511A (en) * | 2021-11-11 | 2021-12-31 | 青岛伊克斯达智能装备有限公司 | Modified pyrolysis carbon black, preparation method thereof and aging-resistant rubber compound |
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| CN111471216A (en) * | 2020-03-30 | 2020-07-31 | 青岛黑猫新材料研究院有限公司 | Modified thermal cracking carbon black |
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