CN116535878A - Modified nano aphanitic graphite powder, preparation method thereof and application thereof in rubber - Google Patents
Modified nano aphanitic graphite powder, preparation method thereof and application thereof in rubber Download PDFInfo
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- CN116535878A CN116535878A CN202310480288.6A CN202310480288A CN116535878A CN 116535878 A CN116535878 A CN 116535878A CN 202310480288 A CN202310480288 A CN 202310480288A CN 116535878 A CN116535878 A CN 116535878A
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 126
- 229920001971 elastomer Polymers 0.000 title claims abstract description 42
- 239000005060 rubber Substances 0.000 title claims abstract description 42
- 238000002360 preparation method Methods 0.000 title claims abstract description 24
- 239000010439 graphite Substances 0.000 claims abstract description 89
- 229910002804 graphite Inorganic materials 0.000 claims abstract description 89
- 239000002002 slurry Substances 0.000 claims abstract description 28
- 238000003756 stirring Methods 0.000 claims abstract description 26
- 238000000227 grinding Methods 0.000 claims abstract description 20
- 239000003607 modifier Substances 0.000 claims abstract description 17
- 239000002994 raw material Substances 0.000 claims abstract description 17
- 238000000034 method Methods 0.000 claims abstract description 15
- 239000002738 chelating agent Substances 0.000 claims abstract description 12
- 238000001035 drying Methods 0.000 claims abstract description 9
- 238000001914 filtration Methods 0.000 claims abstract description 9
- 238000005406 washing Methods 0.000 claims abstract description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000002131 composite material Substances 0.000 claims abstract description 5
- 239000000945 filler Substances 0.000 claims description 16
- 238000005087 graphitization Methods 0.000 claims description 12
- 150000007942 carboxylates Chemical class 0.000 claims description 5
- DPXJVFZANSGRMM-UHFFFAOYSA-N acetic acid;2,3,4,5,6-pentahydroxyhexanal;sodium Chemical compound [Na].CC(O)=O.OCC(O)C(O)C(O)C(O)C=O DPXJVFZANSGRMM-UHFFFAOYSA-N 0.000 claims description 4
- 239000001768 carboxy methyl cellulose Substances 0.000 claims description 4
- 229920000642 polymer Polymers 0.000 claims description 4
- 230000008569 process Effects 0.000 claims description 4
- 235000019812 sodium carboxymethyl cellulose Nutrition 0.000 claims description 4
- 229920001027 sodium carboxymethylcellulose Polymers 0.000 claims description 4
- KXDHJXZQYSOELW-UHFFFAOYSA-N Carbamic acid Chemical compound NC(O)=O KXDHJXZQYSOELW-UHFFFAOYSA-N 0.000 claims description 3
- 229920005552 sodium lignosulfonate Polymers 0.000 claims description 3
- 239000004094 surface-active agent Substances 0.000 claims description 3
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 2
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 2
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 2
- 239000007770 graphite material Substances 0.000 claims 1
- 238000009776 industrial production Methods 0.000 abstract description 3
- 239000000126 substance Substances 0.000 abstract description 3
- 239000000463 material Substances 0.000 abstract description 2
- 230000000052 comparative effect Effects 0.000 description 13
- 239000011159 matrix material Substances 0.000 description 10
- 239000002245 particle Substances 0.000 description 8
- 239000000047 product Substances 0.000 description 8
- 230000008901 benefit Effects 0.000 description 7
- 239000006229 carbon black Substances 0.000 description 7
- 150000001875 compounds Chemical class 0.000 description 6
- 229910052500 inorganic mineral Inorganic materials 0.000 description 6
- 239000011707 mineral Substances 0.000 description 6
- 229920003048 styrene butadiene rubber Polymers 0.000 description 5
- 229920000459 Nitrile rubber Polymers 0.000 description 4
- 238000003917 TEM image Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 238000010298 pulverizing process Methods 0.000 description 4
- 230000003014 reinforcing effect Effects 0.000 description 4
- 239000011435 rock Substances 0.000 description 4
- 229910019142 PO4 Inorganic materials 0.000 description 3
- 238000005054 agglomeration Methods 0.000 description 3
- 230000002776 aggregation Effects 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 239000006185 dispersion Substances 0.000 description 3
- 238000009837 dry grinding Methods 0.000 description 3
- 230000007613 environmental effect Effects 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 239000000706 filtrate Substances 0.000 description 3
- 230000009545 invasion Effects 0.000 description 3
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 3
- 239000010452 phosphate Substances 0.000 description 3
- 238000001878 scanning electron micrograph Methods 0.000 description 3
- DZCAZXAJPZCSCU-UHFFFAOYSA-K sodium nitrilotriacetate Chemical group [Na+].[Na+].[Na+].[O-]C(=O)CN(CC([O-])=O)CC([O-])=O DZCAZXAJPZCSCU-UHFFFAOYSA-K 0.000 description 3
- 238000005303 weighing Methods 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 238000005411 Van der Waals force Methods 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 238000011049 filling Methods 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000001238 wet grinding Methods 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical group C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 229920001732 Lignosulfonate Polymers 0.000 description 1
- 235000021355 Stearic acid Nutrition 0.000 description 1
- 239000002174 Styrene-butadiene Substances 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 150000001491 aromatic compounds Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229920005551 calcium lignosulfonate Polymers 0.000 description 1
- RYAGRZNBULDMBW-UHFFFAOYSA-L calcium;3-(2-hydroxy-3-methoxyphenyl)-2-[2-methoxy-4-(3-sulfonatopropyl)phenoxy]propane-1-sulfonate Chemical compound [Ca+2].COC1=CC=CC(CC(CS([O-])(=O)=O)OC=2C(=CC(CCCS([O-])(=O)=O)=CC=2)OC)=C1O RYAGRZNBULDMBW-UHFFFAOYSA-L 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 230000021615 conjugation Effects 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- YDEXUEFDPVHGHE-GGMCWBHBSA-L disodium;(2r)-3-(2-hydroxy-3-methoxyphenyl)-2-[2-methoxy-4-(3-sulfonatopropyl)phenoxy]propane-1-sulfonate Chemical compound [Na+].[Na+].COC1=CC=CC(C[C@H](CS([O-])(=O)=O)OC=2C(=CC(CCCS([O-])(=O)=O)=CC=2)OC)=C1O YDEXUEFDPVHGHE-GGMCWBHBSA-L 0.000 description 1
- 238000001493 electron microscopy Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000003628 erosive effect Effects 0.000 description 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 1
- 229910021389 graphene Inorganic materials 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 229920005610 lignin Polymers 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000002932 luster Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 1
- HISQRFFCSVGSGI-UHFFFAOYSA-N pentadecane-1,2,3-triol Chemical compound CCCCCCCCCCCCC(O)C(O)CO HISQRFFCSVGSGI-UHFFFAOYSA-N 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 229910052604 silicate mineral Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- 238000009628 steelmaking Methods 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
Classifications
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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
- C09C1/46—Graphite
-
- 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
-
- 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
- C08K9/08—Ingredients agglomerated by treatment with a binding agent
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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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- 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
- C09C3/00—Treatment in general of inorganic materials, other than fibrous fillers, to enhance their pigmenting or filling properties
- C09C3/04—Physical treatment, e.g. grinding, treatment with ultrasonic vibrations
- C09C3/041—Grinding
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- 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
- C09C3/00—Treatment in general of inorganic materials, other than fibrous fillers, to enhance their pigmenting or filling properties
- C09C3/08—Treatment with low-molecular-weight non-polymer organic compounds
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- C09C3/00—Treatment in general of inorganic materials, other than fibrous fillers, to enhance their pigmenting or filling properties
- C09C3/10—Treatment with macromolecular organic compounds
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Abstract
The invention belongs to the fields of chemical industry and materials, and particularly relates to modified nano aphanitic graphite powder, a preparation method thereof and application thereof in rubber. The average diameter of the modified nano aphanitic graphite powder is 100-900 nanometers, the average thickness is 5-50 nanometers, and the specific surface area is 5-40 m 2 And/g. The preparation method comprises the following steps: 1) Will be hiddenThe preparation method comprises the steps of (1) primarily grinding a crystalline graphite raw material, and then adding the ground crystalline graphite raw material into water to prepare aphanitic graphite slurry; 2) Adding a surface modifier into the prepared aphanitic graphite slurry, and grinding and peeling to obtain ground slurry; 3) Adding chelating agent into the ground slurry, stirring, filtering, washing, dehydrating and drying the stirred slurry. The nano aphanitic graphite prepared by the method has small granularity, is not easy to agglomerate, can provide active sites combined with rubber, has low cost and simple steps, can be used for large-scale industrial production, and can fully improve the performances of rubber composites in all aspects.
Description
Technical Field
The invention belongs to the fields of chemical industry and materials, and particularly relates to modified nano aphanitic graphite powder, a preparation method thereof and application thereof in rubber.
Background
The aphanitic graphite is black soil-like mineral with crystal diameter smaller than 1 μm, and specific surface area of the aphanitic graphite is 1-5 m 2 Between/g, which is an aggregate of microcrystalline graphite, the crystals are visible only under electron microscopy, the colour appears grey-black, the luster is darker, the ore appears compact, earthy, lamellar and lamellar. Natural aphanitic graphite ores are generally of higher grade than crystalline flake graphite, but have poor ore selectivity.
The aphanitic graphite has low crystallinity, small crystal grains, overall performance inferior to that of crystalline flake graphite and small application range. The method is mainly used for manufacturing carburant and pencil lead in iron making and steel making at present. The aphanitic graphite resources in China are rich, but the advantages of mineral resources are not fully utilized due to the lower deep processing level of the product, so that a large amount of resources are wasted. If deep processing research can be carried out on the aphanitic graphite, the application range of the aphanitic graphite is increased, and huge social benefit and economic benefit can be generated.
Researches show that the aphanitic graphite as a two-dimensional lamellar mineral has been paid attention to in recent years because of the advantages of small particle size, easy stripping (interlayer binding force is only weak van der Waals force), large specific surface area, good electric conduction and heat conduction properties, environmental protection, no pollution, low price and the like. Because of the similar chemical composition as carbon black, the carbon black is similar to carbon black in microstructure, hardness, high conductivity, stability in oxygen-free erosion medium and the like, so that the carbon black can be partially replaced to be applied to polymers. The aphanitic graphite particles are very fine, the particle diameter reaches the micron level, and the common silicate mineral is difficult to reach even though being ground, and the small particle size makes the aphanitic graphite particles easier to disperse in a rubber matrix, so that the aphanitic graphite is beneficial to improving the performance of rubber products, and therefore, the natural aphanitic graphite used as a rubber filler has great advantages, low cost and environmental protection.
For example, "preparation and performance of modified aphanitic graphite/carbon black/nitrile rubber composite" discloses a method for preparing modified aphanitic graphite/carbon black/nitrile rubber composite by modifying aphanitic graphite with liquid nitrile rubber (LNBR) and mixing with carbon black, NBR and the like.
At present, the preparation of the cryptocrystalline graphite/rubber compound in China mainly develops towards the directions of superfine grinding, organic modification, graphene preparation and the like. The superfine grinding method of aphanitic graphite minerals is mainly divided into dry grinding and wet grinding. The dry ultrafine grinding mainly adopts mechanical impact and high-speed air flow grinding, but the grinding is only carried out by virtue of mutual collision of particles, the grinding degree is low, and secondary agglomeration is extremely easy to occur after grinding, so that the dry grinding effect has a certain limitation. The wet grinding is to use grinding medium to assist grinding and stripping. The particle size after wet pulverization is smaller than that after dry pulverization, but in industrial wet pulverization production, the particle size is usually between 1 and 5 μm, and no report of nano-scale aphanitic graphite products exists.
Thus, there are also problems in the preparation of cryptocrystalline graphite/rubber composites at present, such as: 1) After normal wet stripping, the minerals have a certain agglomeration tendency, so the granularity of the obtained minerals is still larger; 2) The bonding force between the aphanitic graphite and the rubber only depends on Van der Waals force, so that the interfacial bonding force is weak, filler aggregates are easy to form, and the mechanical property of the rubber compound and the construction of a filler network are not facilitated.
In summary, how to obtain nano-scale aphanitic graphite, modify and process aphanitic graphite, improve the dispersion of aphanitic graphite in rubber matrix, and the acting force between aphanitic graphite and rubber matrix, and the like, and further solving the problems is needed.
Disclosure of Invention
The invention aims to provide modified nano aphanitic graphite powder, a preparation method thereof and application thereof in rubber, and aims to provide nano aphanitic graphite powder, which solves the problems that the prior aphanitic graphite has large granularity, is easy to agglomerate, cannot form good dispersion in a rubber matrix and has weak binding force with the rubber matrix.
In order to achieve the purpose of the invention, the invention adopts the following technical scheme:
the modified nano aphanitic graphite powder has average diameter of 100-900 nm, average thickness of 5-50 nm and specific surface area of 5-40 m 2 /g。
The invention also provides a preparation method of the modified nano aphanitic graphite powder, wherein the preparation method comprises the following steps:
1) Primarily grinding a aphanitic graphite raw material, and adding the aphanitic graphite raw material into water to prepare aphanitic graphite slurry;
2) Adding a surface modifier into the prepared aphanitic graphite slurry, and grinding and peeling to obtain ground slurry;
3) Adding chelating agent into the ground slurry for stirring, and filtering, washing, dehydrating and drying the stirred slurry to obtain the modified nano aphanitic graphite powder.
The preparation method comprises the steps of taking aphanitic graphite as a raw material, firstly preparing slurry with a certain concentration, then adding a proper amount of surface modifier for grinding and stripping, utilizing pi-pi conjugation between the surface modifier and the aphanitic graphite to increase the surface hydrophilicity of the aphanitic graphite and the dispersibility in water, then preventing the graphite flake structure from forming an aggregate, then adding a chelating agent for stirring, filtering, washing, dehydrating and drying, and finally obtaining the highly dispersed modified nano aphanitic graphite powder.
Meanwhile, in the invention, by adding the surface modifier and the chelating agent, the aphanitic graphite can be better and finer to be peeled off, so that the nano-grade aphanitic graphite powder is prepared, the interfacial binding force of the filler and the rubber can be increased, the dispersibility of the filler and the rubber in a rubber matrix is improved, agglomeration is prevented, and the physical and mechanical reinforcing performance of the aphanitic graphite powder is improved.
In step 1), the aphanitic graphite raw material is natural aphanitic graphite with different graphitization degrees, preferably natural aphanitic graphite with high graphitization degree, in which DOG is more than 50% and less than 100%, and FWHM (002) is more than 0 and less than 3.
In the present invention, DOG is the degree of graphitization, and FWHM (002) is the full width at half maximum of the (002) peak on the XRD curve of graphite.
Further, in the step 1), the mass concentration of the prepared aphanitic graphite slurry is 5 to 20%.
In step 2), stirring and stripping are carried out by adopting a grinding and stripping machine, wherein the stirring speed is 1000-2350 r/min, the reaction temperature is 20-60 ℃, and the stirring time is 1-3 hours.
Further, in the step 2), the surface modifier is one or more of polyvinylpyrrolidone, sodium carboxymethylcellulose, lignosulfonate or carboxylate type polymer surfactant, and the addition amount of the surface modifier is 1-3% of the mass of the aphanitic graphite raw material.
In the invention, the surface modifier is added to cover polar hydrophilic groups on the surface of graphite, so as to increase the water solubility of the graphite and provide active sites for improving the acting force of a filler-rubber matrix interface.
In the invention, the lignosulfonate is sodium lignosulfonate or calcium lignosulfonate; the carboxylate type polymer surfactant is sodium lignin carboxylate or dodecyl glycerol ether carboxylate.
Further, in the step 3), the chelating agent is one or more of amino carboxylate and organic phosphate, and the addition amount of the chelating agent is 1-3% of the mass of the cryptocrystalline graphite raw material.
In the invention, the amino carboxylate is sodium nitrilotriacetate; the organic phosphate is amino trimethyl fork phosphate.
Further, in the step 3), the stirring speed of stirring is 1000-1500 rpm, and the stirring time is 0.5-1 hour; the washing is to wash the pH value of the filtering solution to 6-8; the drying is carried out at 100-150 ℃ for 12-72 hours.
The invention also provides application of the modified nano aphanitic graphite powder in preparation of rubber.
Specifically, the application is to prepare the nano graphite/rubber compound by taking the modified nano aphanitic graphite powder as a filler and melt blending with rubber.
In the invention, the modified nano aphanitic graphite powder serving as the filler is subjected to modification treatment on the surface in the preparation process, hydrophilic groups are added, and the groups can be used as active sites, so that the interfacial binding force between the filler and the rubber matrix is increased.
In the present invention, the rubber is a variety of rubber commonly used in the art, including but not limited to styrene-butadiene rubber.
Compared with the prior art, the invention has the following advantages:
(1) The modified nano aphanitic graphite powder prepared by adding the surface modifier has the advantages of simple equipment and process, low production cost and high environmental protection, and can be widely applied to industrial production;
(2) Compared with the existing production technology of nano aphanitic graphite, the nano aphanitic graphite produced by the method has small granularity, is not easy to agglomerate, can provide active sites combined with rubber, has low cost and simple steps, can be used for large-scale industrial production, and fully improves the performances of rubber composites in all aspects;
(3) The modified nano aphanitic graphite powder provided by the invention can be used for preparing nano graphite/rubber compound, and can improve the mechanical physical properties, wear resistance, air tightness, electric conduction, heat conduction and other properties of the rubber compound;
(4) When the modified nano aphanitic graphite powder provided by the invention is used for preparing the nano aphanitic graphite/rubber compound, the dispersibility of aphanitic graphite in a rubber matrix is improved, and a filler network structure and the bonding acting force between the filler and the rubber matrix are constructed.
Drawings
FIG. 1 is an SEM image of modified nano-aphanitic graphite powder prepared in example 1 of the present invention;
FIG. 2 is an SEM image of unmodified nano-aphanitic graphite powder prepared in comparative example 3;
FIG. 3 is a TEM image of a modified nano-aphanitic graphite/rubber slice prepared in example 1 of the present invention;
FIG. 4 is a TEM image of unmodified nano-aphanitic graphite/rubber slices prepared in comparative example 3;
Detailed Description
The following are specific embodiments of the present invention, which are described in order to further illustrate the invention, not to limit the invention.
Example 1
1) Selecting high graphitization degree aphanitic graphite with dog= 83.72% and FWHM (002) =0.49 in a magical rock invasion environment as a raw material, primarily grinding, weighing 150g of ground aphanitic graphite, adding into 1500ml of water, and preparing aphanitic graphite slurry with the mass concentration of 10%;
2) Adding 1.5g of sodium carboxymethyl cellulose serving as a surface modifier into the prepared aphanitic graphite slurry, stirring and stripping in a mill stripper, wherein the stirring speed is 2350 r/min, the reaction temperature is 40 ℃, and the stirring time is 1 hour, so as to obtain milled slurry;
3) Adding 1.5g of chelating agent sodium nitrilotriacetate into the ground slurry, stirring for 1 hour at the rotation speed of 1000 rpm, and filtering, washing and dehydrating on a vacuum filter after stirring until the pH value of the filtrate reaches 6-8; and then drying for 24 hours at 120 ℃ to obtain the modified nano aphanitic graphite powder.
The modified nano aphanitic graphite powder obtained in this example had an average diameter of 600 nm, an average thickness of 30 nm and a specific surface area of 36.04m 2 And/g, the SEM of which is shown in FIG. 1.
Example 2
The embodiment is characterized by high graphitization generated by the intrusion of the magma rock into the coal seam in different areasNano aphanitic graphite (dog=80.23, fwhm=0.563) was prepared as similar to example 1 except that the surface modifier used in step 2) was sodium lignin sulfonate, and the obtained nano aphanitic graphite ore was similar to the product obtained by the process of example 1, having an average diameter of 650 nm, an average thickness of 25 nm, and a specific surface area of 35.3m 2 /g。
Examples 3 to 8
The preparation process of the modified nano aphanitic graphite powder described in examples 3 to 8 is described in detail below in the form of a list.
TABLE 1 preparation of nano aphanitic graphite products
Comparative example 1
In this example, nano aphanitic graphite was prepared from aphanitic graphite (semi-graphite) having a low degree of graphitization (dog=39.77, fwhm (002) =4.703) as a raw material, and the preparation method was the same as in example 1, except that the aphanitic graphite had a low degree of graphitization, a partially block-shaped disordered domain aromatic compound structure, and the sample was less likely to be exfoliated as compared with aphanitic graphite having a high degree of graphitization, and the modified nano aphanitic graphite powder finally obtained had an average diameter of 1.25 μm, an average thickness of 200nm, and a specific surface area of 13.6m 2 /g。
Comparative example 2
The raw material 100g used in example 1 was used and pulverized in a high-speed pulverizer at a rotational speed of 2000 rpm for 30 minutes to obtain a product having an average diameter of 2 μm, an average thickness of 500 nm and a specific surface area of 10.4m 2 And/g. Thus, it was demonstrated that a large amount of aggregates still exist using conventional solid phase mechanical pulverization methods.
Comparative example 3
This example is directed to example 1, and differs from example 1 in that no surface modifier is added during the preparation process for treatment, as follows:
1) Selecting high graphitization degree aphanitic graphite with dog= 77.91% and FWHM (002) =0.502 in a magical rock invasion environment as a raw material, primarily grinding, weighing 150g of ground aphanitic graphite, adding into 1500ml of water, and preparing aphanitic graphite slurry with the mass concentration of 10%;
2) Adding 1.5g of chelating agent sodium nitrilotriacetate into the prepared aphanitic graphite slurry, stirring for 1 hour at the rotation speed of 1000 rpm, and filtering, washing and dehydrating on a vacuum filter after stirring until the pH value of the filtrate reaches 6-8; and then drying for 24 hours at 120 ℃ to obtain the modified nano aphanitic graphite powder.
The average diameter of the modified nano aphanitic graphite powder obtained in the comparative example is 950 nanometers, the average thickness is 70 nanometers, and the specific surface area is 20.02m 2 And/g. The SEM image is shown in fig. 2, from which it can be seen that the filler has a larger average diameter and thickness.
Comparative example 4
This example is directed to example 1, and differs from example 1 in that no chelating agent is added during the preparation process for treatment, specifically as follows:
1) Selecting high graphitization degree aphanitic graphite with dog= 77.91% and FWHM (002) =0.502 in a magical rock invasion environment as a raw material, primarily grinding, weighing 150g of ground aphanitic graphite, adding into 1500ml of water, and preparing aphanitic graphite slurry with the mass concentration of 10%;
2) Adding 1.5g of sodium carboxymethyl cellulose serving as a surface modifier into the prepared aphanitic graphite slurry, stirring and stripping in a mill stripper, wherein the stirring speed is 2350 r/min, the reaction temperature is 40 ℃, and the stirring time is 2 hours, so as to obtain milled slurry; filtering, washing and dehydrating the ground slurry on a vacuum filter until the pH value of the filtrate reaches 6-8; and then drying for 24 hours at 120 ℃ to obtain the modified nano aphanitic graphite powder.
The modified nano aphanitic graphite powder obtained in this exampleAn average diameter of 724 nm, an average thickness of 36 nm, and a specific surface area of 28.27m 2 /g。
Application examples
The nano aphanitic graphite product prepared by the invention is used for filling styrene-butadiene rubber and performing performance reinforcing experiments. The samples made in the comparative examples were compared as a comparative group. The rubber experimental formula is as follows: 100 parts of SBR; 3 parts of zinc oxide; 1 part of stearic acid; 1 part of accelerator; 1.75 parts of sulfur; 50 parts of filler (modified nano aphanitic graphite powder prepared in examples 1-2 and comparative examples 1-4). The experiment adopts a rotor-free vulcanizing machine, and the vulcanizing temperature is 153 ℃. The tensile tester is A1-7000GD, and the abrasion performance is tested by using a DIN roller tester. The test results are shown in the following table 2, and fig. 3 is a TEM image of the filler/rubber section corresponding to example 1; fig. 4 is a TEM image of the filler/rubber section corresponding to comparative example 3, and it can be seen from fig. 4 that the average filler diameter and thickness are large.
Table 2, styrene-butadiene rubber comparative experiment results
The results show (Table 2) that the product of the invention is used for filling and reinforcing styrene-butadiene rubber, and has greatly improved mechanical and physical properties such as tensile strength, tearing strength, 100% stretching strength, 300% stretching strength, elongation at break, wear resistance and the like, and shows the abrupt change effect of nano materials, thus having great practical application value. As a comparative example, the dispersion effect was poor due to the dry milling effect, no modifier added, no chelating agent added, etc., and the mechanical and physical reinforcing properties were inferior to those of the present invention.
Claims (10)
1. A modified nano aphanitic graphite powder is characterized in that the average diameter of the modified nano aphanitic graphite powder is 100-900 nanometers, the average thickness is 5-50 nanometers, and the specific surface area is 5-40 m 2 /g。
2. A method for preparing the modified nano aphanitic graphite powder of claim 1, wherein the method comprises the following steps:
1) Primarily grinding a aphanitic graphite raw material, and then adding the ground aphanitic graphite raw material into water to prepare aphanitic graphite slurry;
2) Adding a surface modifier into the prepared aphanitic graphite slurry, and grinding and peeling to obtain ground slurry;
3) Adding chelating agent into the ground slurry for stirring, and filtering, washing, dehydrating and drying the stirred slurry to obtain the modified nano aphanitic graphite powder.
3. The process according to claim 2, wherein in step 1), the aphanitic graphite material is natural aphanitic graphite with various graphitization degrees, preferably natural aphanitic graphite with high graphitization degree of 50% < DOG < 100%,0 < FWHM (002) < 3.
4. The method according to claim 2, wherein the aphanitic graphite slurry prepared in step 1) has a mass concentration of 5 to 20%.
5. The method according to claim 2, wherein in step 2), the stirring and peeling are performed by a peeling machine, the stirring speed is 1000-2350 rpm, the reaction temperature is 20-60 ℃, and the stirring time is 1-3 hours.
6. The preparation method of claim 2, wherein in the step 2), the surface modifier is one or more of polyvinylpyrrolidone, sodium carboxymethylcellulose, lignosulfonate or carboxylate type polymer surfactant, and the addition amount of the surface modifier is 1-3% of the mass of the cryptocrystalline graphite raw material.
7. The preparation method according to claim 2, wherein in the step 3), the chelating agent is one or more of aminocarboxylate and organophosphate, and the addition amount thereof is 1-3% of the mass of the cryptocrystalline graphite raw material.
8. The method according to claim 2, wherein in the step 3), the stirring speed of the stirring is 1000 to 1500 rpm, and the stirring time is 0.5 to 1 hour; the washing is to wash the pH value of the filtering solution to 6-8; the drying is carried out at 100-150 ℃ for 12-72 hours.
9. Use of the modified nano aphanitic graphite powder of claim 1 in the preparation of rubber.
10. The use according to claim 9, characterized in that the modified nano aphanitic graphite powder according to claim 1 is used as filler and is melt blended with rubber to prepare nano graphite/rubber composite.
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