CN111909546A - Graphene modified waste tire thermal cracking carbon black composite material and preparation method thereof - Google Patents
Graphene modified waste tire thermal cracking carbon black composite material and preparation method thereof Download PDFInfo
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- 239000006229 carbon black Substances 0.000 title claims abstract description 83
- 238000004227 thermal cracking Methods 0.000 title claims abstract description 77
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 75
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 69
- 239000010920 waste tyre Substances 0.000 title claims abstract description 40
- 238000002360 preparation method Methods 0.000 title claims abstract description 30
- 239000002131 composite material Substances 0.000 title claims description 51
- 238000000034 method Methods 0.000 claims abstract description 30
- 239000000463 material Substances 0.000 claims abstract description 21
- 238000002156 mixing Methods 0.000 claims abstract description 15
- 238000010438 heat treatment Methods 0.000 claims abstract description 12
- 239000002114 nanocomposite Substances 0.000 claims abstract description 7
- 230000020477 pH reduction Effects 0.000 claims abstract description 7
- 239000000126 substance Substances 0.000 claims abstract description 7
- 239000007900 aqueous suspension Substances 0.000 claims abstract description 6
- 230000008569 process Effects 0.000 claims abstract description 6
- 238000007385 chemical modification Methods 0.000 claims abstract description 4
- 238000000746 purification Methods 0.000 claims abstract description 3
- 239000006185 dispersion Substances 0.000 claims description 35
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 33
- 239000007788 liquid Substances 0.000 claims description 19
- 239000011259 mixed solution Substances 0.000 claims description 11
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 8
- 230000007935 neutral effect Effects 0.000 claims description 8
- 238000005406 washing Methods 0.000 claims description 8
- 239000002253 acid Substances 0.000 claims description 7
- 229910002804 graphite Inorganic materials 0.000 claims description 7
- 239000010439 graphite Substances 0.000 claims description 7
- 239000002270 dispersing agent Substances 0.000 claims description 6
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 claims description 6
- 230000004048 modification Effects 0.000 claims description 6
- 238000012986 modification Methods 0.000 claims description 6
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 claims description 6
- 239000007822 coupling agent Substances 0.000 claims description 5
- 238000005336 cracking Methods 0.000 claims description 4
- 239000002002 slurry Substances 0.000 claims description 4
- 238000001694 spray drying Methods 0.000 claims description 4
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims description 2
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 2
- 238000001914 filtration Methods 0.000 claims description 2
- 238000009775 high-speed stirring Methods 0.000 claims description 2
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 2
- 239000000203 mixture Substances 0.000 abstract description 3
- 238000005054 agglomeration Methods 0.000 abstract 1
- 230000002776 aggregation Effects 0.000 abstract 1
- 229920001971 elastomer Polymers 0.000 description 33
- 238000006243 chemical reaction Methods 0.000 description 12
- 239000000047 product Substances 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 9
- 244000043261 Hevea brasiliensis Species 0.000 description 8
- 229920003052 natural elastomer Polymers 0.000 description 8
- 229920001194 natural rubber Polymers 0.000 description 8
- 238000003756 stirring Methods 0.000 description 7
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 4
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- 239000008367 deionised water Substances 0.000 description 4
- 229910021641 deionized water Inorganic materials 0.000 description 4
- 238000007599 discharging Methods 0.000 description 4
- 239000012286 potassium permanganate Substances 0.000 description 4
- 238000003825 pressing Methods 0.000 description 4
- 239000000725 suspension Substances 0.000 description 4
- 238000004140 cleaning Methods 0.000 description 3
- 239000000945 filler Substances 0.000 description 3
- 238000010408 sweeping Methods 0.000 description 3
- 239000012752 auxiliary agent Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 239000011787 zinc oxide Substances 0.000 description 2
- 241000282414 Homo sapiens Species 0.000 description 1
- 239000004594 Masterbatch (MB) Substances 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 125000003636 chemical group Chemical group 0.000 description 1
- 238000005536 corrosion prevention Methods 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- -1 graphite alkene Chemical class 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 230000033116 oxidation-reduction process Effects 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 239000012763 reinforcing filler Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 239000002910 solid waste Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000012795 verification Methods 0.000 description 1
- 239000004636 vulcanized rubber Substances 0.000 description 1
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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
- C09C1/482—Preparation from used rubber products, e.g. tyres
-
- 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
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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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- 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
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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
- C09C1/58—Agglomerating, pelleting, or the like by wet methods
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- C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
- C09C3/00—Treatment in general of inorganic materials, other than fibrous fillers, to enhance their pigmenting or filling properties
- C09C3/006—Combinations of treatments provided for in groups C09C3/04 - C09C3/12
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- C09C3/00—Treatment in general of inorganic materials, other than fibrous fillers, to enhance their pigmenting or filling properties
- C09C3/04—Physical treatment, e.g. grinding, treatment with ultrasonic vibrations
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- C09C3/00—Treatment in general of inorganic materials, other than fibrous fillers, to enhance their pigmenting or filling properties
- C09C3/04—Physical treatment, e.g. grinding, treatment with ultrasonic vibrations
- C09C3/043—Drying, calcination
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- C09C3/00—Treatment in general of inorganic materials, other than fibrous fillers, to enhance their pigmenting or filling properties
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- C09C3/00—Treatment in general of inorganic materials, other than fibrous fillers, to enhance their pigmenting or filling properties
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- Compositions Of Macromolecular Compounds (AREA)
- Separation, Recovery Or Treatment Of Waste Materials Containing Plastics (AREA)
- Tires In General (AREA)
Abstract
The invention discloses a preparation method of a graphene modified waste tire thermal cracking carbon black nano composite material, which mainly comprises the steps of preparing graphene oxide, preparing a thermal cracking carbon black water suspension, carrying out wet blending, acidification, purification and chemical modification on the graphene oxide and the thermal cracking carbon black water suspension, and finally carrying out post-treatment and high-temperature heat treatment on the mixture to obtain a product, wherein the ash content in the thermal cracking carbon black of a waste tire in the finally obtained product is greatly reduced, and the graphene oxide forms a chemical bonding joint on the surface of the carbon black after the chemical modification, so that the agglomeration problem caused by the independent addition of the graphene can be avoided in the use process, and the graphene makes up for the performance loss caused by the independent use of the thermal cracking carbon black.
Description
Technical Field
The invention relates to a preparation method of an auxiliary agent for rubber, and particularly relates to a preparation method of a graphene grafted modified waste tire thermal cracking carbon black nano composite material.
Background
China is a large country for producing and using tires, the production amount of waste tires is huge every year, the treatment mode generally adopts the treatment mode of solid wastes, such as accumulation, burying and the like, the living environment of people is seriously polluted, even the health of human beings is influenced, and a more favorable treatment mode is a problem to be solved urgently. The thermal cracking treatment of the waste tires is considered as an effective recycling treatment mode, which not only can dispose the tires, but also can recycle certain materials. The waste tire thermal cracking carbon black is one of main products of thermal cracking, and how to make the waste tire thermal cracking carbon black be efficiently and comprehensively utilized is a crucial step in the recovery process. The apparent appearance of the carbon black for the tire is not completely reduced in the thermal cracking process, and a large amount of ash exists, so that the carbon black cannot be reused in the tire or other rubber products.
Graphene has excellent functionality, related products of graphene are applied to the market at present, excellent service performance of graphene is exerted in the fields of strength, heat conduction, electric conduction, corrosion prevention and the like, and large-scale industrial application of graphene in the field of rubber is not achieved for a while. Although products such as graphene masterbatch are popularized to tires and partial rubber products in a small amount at present, the cost control by combining with the rubber industry is still difficult to form a large-scale market share based on the high price. Therefore, the method seeks to develop a product with high cost performance by combining the performances of the graphene, and has great practical significance for the popularization of the graphene in the rubber industry and other markets.
Through a large amount of experimental verification in earlier stage, we find that mechanical properties can appear when junked tire thermal cracking carbon black is applied to positions such as tread, side wall and descend, wear resistance descends, the themogenesis reduces, phenomenons such as hardness reduction, and promotion and reduction of these performances can form complementarily with the performance that graphite alkene embodies when using in the tire just, if can form the organic combination with the two, hope to replace the performance of original material in the tire, can obtain the performance promotion even, and can balance its comprehensive use cost, thereby realize the application of both in tire and other rubber products.
Disclosure of Invention
The invention aims to provide a preparation method of a graphene grafted and modified waste tire thermal cracking carbon black nano composite material for rubber, wherein a large amount of acid is contained in an intermediate product when graphene is prepared by an oxidation-reduction method, ash in the waste tire thermal cracking carbon black can be greatly removed by adding the waste tire thermal cracking carbon black, more oxygen-containing groups on the surface of the carbon black are provided, the defect that the acid is difficult to industrialize in the modification process of the waste tire thermal cracking carbon black is avoided, the surface of the thermal cracking carbon black and the graphene oxide can form chemical bonding by adding a coupling agent and adjusting different production processes, the dispersion of the graphene is promoted, and the product comprehensively utilizes the low cost of the thermal cracking carbon black and the performance compensation of the graphene, so that the application values of the thermal cracking carbon black and the.
1. A preparation method of a graphene modified waste tire thermal cracking carbon black nano composite material is characterized by comprising the following steps:
a. preparing a graphene oxide dispersion liquid: preparing an aqueous dispersion of graphene oxide by using natural crystalline flake graphite by using a Hummers method;
b. preparation and acidification of thermal cracking carbon black aqueous suspension: adding waste tire thermal cracking carbon black into water according to a certain proportion, adding an auxiliary dispersing agent, treating for 10 minutes under the condition of high-speed stirring, adding sulfuric acid, adjusting the pH of a water dispersion liquid to be 2-4, and treating for 1 hour at 60 ℃ to obtain an acidified thermal cracking carbon black water suspension;
c. wet blending, chemical grafting modification: mixing a and b together according to different proportions, then adjusting the pH of the system to about 4, adding a coupling agent, adjusting the temperature to 70 ℃, and reacting for 4 hours to complete chemical grafting;
d. purification and high-temperature heat treatment: and c, filtering the mixed solution obtained in the step c, washing with water to obtain neutral water slurry, and performing high-temperature spray drying on the neutral water slurry to obtain a final product of the nano composite material.
2. A method of preparing a composite material according to claim 1, wherein: the auxiliary dispersant is one of sodium dodecyl benzene sulfonate, cetyl trimethyl ammonium bromide and polyvinyl alcohol.
3. A method of preparing a composite material according to claim 1, wherein: the dosage of the auxiliary dispersant is 1 to 10 weight percent of the thermal cracking carbon black.
4. A method of preparing a composite material according to claim 1, wherein: the concentration of the cracking carbon black in the water dispersion liquid is 10-50%.
5. A method of preparing a composite material according to claim 1, wherein: the mass ratio of the graphene oxide to the thermal cracking carbon black is 1: 200-1: 50.
6. A method of preparing a composite material according to claim 1, wherein: the coupling agent used for chemical modification comprises one of Si69, KH550 and KH 570.
7. A method of preparing a composite material according to claim 1, wherein: the air inlet temperature in the high-temperature spray drying process is 300-600 ℃.
8. A method of preparing a composite material according to claim 1, wherein: the used waste tire thermal cracking carbon black is low-temperature thermal cracking carbon black, and the thermal cracking temperature is 300-400 ℃.
Compared with the prior art, the invention has the advantages that:
(1) the carbon material composite auxiliary agent for rubber can be obtained by the invention, so that the graphene and the waste tire thermal cracking carbon black are organically combined, the surface of the waste tire thermal cracking carbon black is optimized, the interaction with a rubber material is improved, and the product performance is optimized.
(2) The process combines the characteristic that the intermediate graphene oxide contains a large amount of acid sources in the earlier preparation process of the graphene, effectively removes the surface ash of the thermal cracking carbon black through process optimization, and provides enough chemical groups so as to form effective bonding with the graphene oxide, thereby endowing the graphene oxide with functionality. The preparation process of the product is energy-saving, green and efficient, and can be popularized and industrialized.
(3) The product balances the difference between the high cost of graphene and the low cost of thermal cracking carbon black, the obtained composite material has lower cost than the currently applied reinforcing filler, and the performance is further optimized during application.
Detailed Description
The present invention will be described in further detail with reference to examples. It should be noted that the following examples are only for illustrating the present invention and should not be construed as limiting the scope of the present invention, and those skilled in the art can make modifications and variations of the present invention without departing from the scope of the present invention.
Comparative example 1
According to a basic rubber formula 1 shown in Table 1, 5 parts of common zinc oxide is added, and a natural rubber composite material is prepared by a conventional mixing method, wherein the preparation process comprises the following steps: adding natural rubber to the internal mixer → adding 2/3 filler → adding 1/3 filler → sweeping → adding small materials except for the vulcanizing agent → sweeping → discharging rubber, and adding a segment of rubber to the internal mixer after the segment is parked for more than 4 hours → adding the vulcanizing agent → sweeping → discharging rubber to obtain the rubber of comparative example 1.
Comparative example 2
According to a basic rubber formula 2 shown in Table 1, 5 parts of common zinc oxide is added, and a natural rubber composite material is prepared by a conventional mixing method, wherein the preparation process comprises the following steps: adding natural rubber to the internal mixer → adding filler → adding thermal cracking carbon black → cleaning → adding small materials except the vulcanizing agent → cleaning → discharging rubber, and adding a section of rubber to the internal mixer → adding the vulcanizing agent → cleaning → discharging rubber after a section is parked for more than 4 hours to obtain the rubber of the comparative example 2.
Wherein the ash content of the thermal cracking carbon black used is 18%.
Example 1
A preparation method of a graphene modified waste tire thermal cracking carbon black composite material comprises the following specific preparation processes:
(1) preparing an aqueous dispersion of graphene oxide: adding 1g of NaCl-treated expanded graphite and 25mL of concentrated sulfuric acid into a 250mL flask, stirring at room temperature for 4 hours, heating the container to 40 ℃, adding 100mg of NANO3 and 500mg of potassium permanganate, continuously adding water, keeping constant temperature reaction for 2 hours, and then adding water and 10mL of 30% hydrogen peroxide solution to terminate the reaction, thereby obtaining the graphene oxide aqueous dispersion.
(2) Preparing thermal cracking carbon black water dispersion liquid and carrying out acidification treatment: adding 200g of waste tire thermal cracking carbon black into an aqueous solution containing 1% of sodium dodecyl benzene sulfonate, and stirring at a constant temperature and a high speed for 30 minutes at 40 ℃ to obtain the stable thermal cracking carbon black aqueous dispersion.
(3) Preparation of the two-phase composite material: and (3) respectively adding the dispersion liquid obtained in the step (1) and the dispersion liquid obtained in the step (2) into a container, raising the temperature of a mixed system to 70 ℃, adding water to adjust the pH of the system to 2-4, adding KH550, and continuously reacting for 4 hours.
(4) And after the reaction is finished, performing filter pressing treatment on the mixed solution, respectively washing the mixed solution repeatedly by using 5% dilute hydrochloric acid and deionized water, and performing high-temperature 600 ℃ heat treatment on the obtained neutral suspension to obtain the graphene modified waste tire thermal cracking carbon black composite material.
The mass ratio of the graphene to the thermal cracking carbon black in the graphene-modified waste tire thermal cracking carbon black composite material obtained in the example 1 is about 1: 200, and the ash content of the composite material is 6.3% by detection.
According to a basic rubber formula 3 shown in Table 1, 10 parts of the graphene composite material prepared in the embodiment is added, a natural rubber composite material is prepared by a conventional mixing method, the preparation process is the same as that of the comparative example 1, and the rubber of the embodiment 1 is obtained by mixing.
Example 2
A preparation method of a graphene modified waste tire thermal cracking carbon black composite material comprises the following specific preparation processes:
(1) preparing an aqueous dispersion of graphene oxide: adding 1g of expanded graphite treated by NACl and 25mL of concentrated sulfuric acid into a 250mL flask, stirring for 4 hours at room temperature, heating the container to 40 ℃, adding 100mg of NANO3 and 500mg of potassium permanganate, continuously adding water, keeping constant temperature reaction for 2 hours, and then adding water and 10mL of 30% hydrogen peroxide solution to terminate the reaction, thereby obtaining the graphene oxide aqueous dispersion.
(2) Preparing thermal cracking carbon black water dispersion liquid and carrying out acidification treatment: 100g of waste tire thermal cracking carbon black is added into an aqueous solution containing 1 percent of sodium dodecyl benzene sulfonate, and the mixture is stirred at a constant temperature and a high speed for 30 minutes at 40 ℃ to obtain a stable thermal cracking carbon black water dispersion.
(3) Preparation of the two-phase composite material: and (3) respectively adding the dispersion liquid obtained in the step (1) and the dispersion liquid obtained in the step (2) into a container, raising the temperature of a mixed system to 70 ℃, adding water to adjust the pH of the system to 2-4, adding KH550, and continuously reacting for 4 hours.
(4) And after the reaction is finished, performing filter pressing treatment on the mixed solution, respectively washing the mixed solution repeatedly by using 5% dilute hydrochloric acid and deionized water, and performing high-temperature 600 ℃ heat treatment on the obtained neutral suspension to obtain the graphene modified waste tire thermal cracking carbon black composite material.
The mass ratio of the graphene to the thermal cracking carbon black in the graphene modified waste tire thermal cracking carbon black composite material obtained in the embodiment 2 is about 1: 100. The ash content of the obtained material is detected to be 6.7%.
According to the basic rubber formula 4 shown in table 1, 12 parts of the graphene composite material prepared in the example is added, and a natural rubber composite material is prepared by a conventional mixing method, and the preparation process is the same as that of the comparative example 1, and the rubber of the example 2 is obtained by mixing.
Example 3
A preparation method of a graphene modified waste tire thermal cracking carbon black composite material comprises the following specific preparation processes:
(1) preparing an aqueous dispersion of graphene oxide: adding 1g of expanded graphite treated by NACl and 25mL of concentrated sulfuric acid into a 250mL flask, stirring for 4 hours at room temperature, heating the container to 40 ℃, adding 100mg of NANO3 and 500mg of potassium permanganate, continuously adding water, keeping constant temperature reaction for 2 hours, and then adding water and 10mL of 30% hydrogen peroxide solution to terminate the reaction, thereby obtaining the graphene oxide aqueous dispersion.
(2) Preparing thermal cracking carbon black water dispersion liquid and carrying out acidification treatment: adding 50g of waste tire thermal cracking carbon black into an aqueous solution containing 1% of sodium dodecyl benzene sulfonate, and stirring at a constant temperature and a high speed for 30 minutes at 40 ℃ to obtain the stable thermal cracking carbon black aqueous dispersion.
(3) Preparation of the two-phase composite material: and (3) respectively adding the dispersion liquid obtained in the step (1) and the dispersion liquid obtained in the step (2) into a container, raising the temperature of a mixed system to 70 ℃, adding water to adjust the pH of the system to 2-4, adding KH550, and continuously reacting for 4 hours.
(4) And after the reaction is finished, performing filter pressing treatment on the mixed solution, respectively washing the mixed solution repeatedly by using 5% dilute hydrochloric acid and deionized water, and performing high-temperature 600 ℃ heat treatment on the obtained neutral suspension to obtain the graphene modified waste tire thermal cracking carbon black composite material.
The mass ratio of the graphene to the thermal cracking carbon black in the graphene modified waste tire thermal cracking carbon black composite material obtained in the embodiment 3 is about 1: 50. The ash content of the obtained material is detected to be 6.1%.
According to a basic rubber formula 5 shown in Table 1, 12 parts of the graphene composite material prepared in the embodiment is added, a natural rubber composite material is prepared by a conventional mixing method, the preparation process is the same as that of the comparative example 1, and the rubber of the embodiment 3 is obtained by mixing.
Example 4
A preparation method of a graphene modified waste tire thermal cracking carbon black composite material comprises the following specific preparation processes:
(1) preparing an aqueous dispersion of graphene oxide: adding 1g of expanded graphite treated by NACl and 25mL of concentrated sulfuric acid into a 250mL flask, stirring for 4 hours at room temperature, heating the container to 40 ℃, adding 100mg of NANO3 and 500mg of potassium permanganate, continuously adding water, keeping constant temperature reaction for 2 hours, and then adding water and 10mL of 30% hydrogen peroxide solution to terminate the reaction, thereby obtaining the graphene oxide aqueous dispersion.
(2) Preparing thermal cracking carbon black water dispersion liquid and carrying out acidification treatment: adding 50g of waste tire thermal cracking carbon black into an aqueous solution containing 1% of sodium dodecyl benzene sulfonate, and stirring at a constant temperature and a high speed for 30 minutes at 40 ℃ to obtain the stable thermal cracking carbon black aqueous dispersion.
(3) Preparation of the two-phase composite material: and (3) respectively adding the dispersion liquid obtained in the step (1) and the dispersion liquid obtained in the step (2) into a container, heating the temperature of the mixed system to 70 ℃, adding water to adjust the pH of the system to 2-4, adding Si-69, and continuing to react for 4 hours.
(4) And after the reaction is finished, performing filter pressing treatment on the mixed solution, respectively washing the mixed solution repeatedly by using 5% dilute hydrochloric acid and deionized water, and performing high-temperature 600 ℃ heat treatment on the obtained neutral suspension to obtain the graphene modified waste tire thermal cracking carbon black composite material.
The mass ratio of the graphene to the thermal cracking carbon black in the graphene modified waste tire thermal cracking carbon black composite material obtained in the embodiment 1 is about 1: 50. The ash content of the obtained material is 5.7 percent through detection.
According to a basic rubber formula 6 shown in Table 1, 12 parts of the graphene composite material prepared in the example is added, a natural rubber composite material is prepared by a conventional mixing method, the preparation process is the same as that of the comparative example 1, and the rubber of the example 4 is obtained by mixing.
TABLE 1 basic rubber test formulation
TABLE 2 Properties of NR composites
Table 2 shows the properties of the NR composite material prepared by adding the graphene-modified thermal cracking carbon black composite material prepared in examples 1 to 4, and it can be found by comparing the rubber compound data of comparative examples 1 and 2 that when the N234 carbon black is replaced by the waste tire thermal cracking carbon black alone, the hardness, the mechanical property, and the wear resistance are greatly lost and cannot meet the use conditions of the material, and after the graphene modification, the mechanical property and the wear resistance of the composite material equivalent to the N234 carbon black rubber compound are improved to different degrees because the acid in the graphene oxide dispersion liquid and the subsequent acid washing process convert a large amount of ash in the cracking carbon black into soluble salts, thereby reducing the ash in the material, and in addition, the acid washing improves the surface functional group content of the carbon black, thereby forming a chemical bonding with the graphene, and promoting the dispersion of each other, the combination compatibility of the graphene and the rubber is greatly improved, the crosslinking density of vulcanized rubber is improved, and the addition of the graphene compensates the performance loss of the cracking carbon black, so that the comprehensive performance reaches or exceeds the performance of the original N234. Therefore, the mechanical property and the abrasion performance of the rubber material can be improved by replacing the graphene modified waste tire thermal cracking carbon black composite auxiliary material with a small amount of the graphene modified waste tire thermal cracking carbon black composite auxiliary material, and the use cost of the material can be reduced.
The above-mentioned embodiments are merely illustrative of the preferred embodiments of the present invention, and do not limit the scope of the present invention, and various modifications and improvements of the technical solution of the present invention by those skilled in the art should fall within the protection scope defined by the claims of the present invention without departing from the spirit of the present invention.
Claims (8)
1. A preparation method of a graphene modified waste tire thermal cracking carbon black nano composite material is characterized by comprising the following steps:
a. preparing a graphene oxide dispersion liquid: preparing an aqueous dispersion of graphene oxide by using natural crystalline flake graphite by using a Hummers method;
b. preparation and acidification treatment of thermal cracking carbon black aqueous suspension: adding waste tire thermal cracking carbon black into water according to a certain proportion, adding an auxiliary dispersing agent, treating for 10 minutes under the condition of high-speed stirring, adding sulfuric acid, adjusting the pH of a water dispersion liquid to be 2-4, and treating for 1 hour at 60 ℃ to obtain an acidified thermal cracking carbon black water suspension;
c. wet blending, chemical grafting modification: mixing a and b together according to different proportions, then adjusting the pH of the system to about 4, adding a coupling agent, adjusting the temperature to 70 ℃, and reacting for 4 hours to complete chemical grafting;
d. purification and high-temperature heat treatment: and c, filtering the mixed solution obtained in the step c, washing the mixed solution with acid and water to obtain neutral water slurry, and performing high-temperature spray drying on the neutral water slurry to obtain a final nano composite material product.
2. A method of preparing a composite material according to claim 1, wherein: the auxiliary dispersant is one of sodium dodecyl benzene sulfonate, cetyl trimethyl ammonium bromide and polyvinyl alcohol.
3. A method of preparing a composite material according to claim 1, wherein: the dosage of the auxiliary dispersant is 1 to 10 weight percent of the thermal cracking carbon black.
4. A method of preparing a composite material according to claim 1, wherein: the concentration of the cracking carbon black in the water dispersion liquid is 10-50%.
5. A method of preparing a composite material according to claim 1, wherein: the mass ratio of the graphene oxide to the thermal cracking carbon black is 1: 200-1: 50.
6. A method of preparing a composite material according to claim 1, wherein: the coupling agent used for chemical modification comprises one of Si69, KH550 and KH 570.
7. A method of preparing a composite material according to claim 1, wherein: the air inlet temperature in the high-temperature spray drying process is 300-600 ℃.
8. A method of preparing a composite material according to claim 1, wherein: the used waste tire thermal cracking carbon black is low-temperature thermal cracking carbon black, and the thermal cracking temperature is 300-400 ℃.
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| CN114213721A (en) * | 2021-12-29 | 2022-03-22 | 青岛双星轮胎工业有限公司 | Rubber composition and preparation method thereof |
| CN114836059A (en) * | 2022-05-11 | 2022-08-02 | 宁波卡利特新材料有限公司 | Low-odor carbon black composite filler and preparation method thereof |
| WO2024016090A1 (en) * | 2022-07-22 | 2024-01-25 | Sustrend Laboratorios Spa | Process for obtaining anode-grade graphitic carbon for batteries from by-products generated from recycled tyres and graphitic carbon obtained from the process |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN114213721A (en) * | 2021-12-29 | 2022-03-22 | 青岛双星轮胎工业有限公司 | Rubber composition and preparation method thereof |
| CN114836059A (en) * | 2022-05-11 | 2022-08-02 | 宁波卡利特新材料有限公司 | Low-odor carbon black composite filler and preparation method thereof |
| CN114836059B (en) * | 2022-05-11 | 2023-09-01 | 宁波卡利特新材料有限公司 | Low-odor carbon black composite filler and preparation method thereof |
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