CN115873424A - Carbon nano tube modified particle and preparation method and application thereof - Google Patents
Carbon nano tube modified particle and preparation method and application thereof Download PDFInfo
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- CN115873424A CN115873424A CN202211511026.3A CN202211511026A CN115873424A CN 115873424 A CN115873424 A CN 115873424A CN 202211511026 A CN202211511026 A CN 202211511026A CN 115873424 A CN115873424 A CN 115873424A
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 121
- 239000002041 carbon nanotube Substances 0.000 title claims abstract description 104
- 229910021393 carbon nanotube Inorganic materials 0.000 title claims abstract description 104
- 239000002245 particle Substances 0.000 title claims abstract description 96
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- 239000000463 material Substances 0.000 claims abstract description 29
- 239000011268 mixed slurry Substances 0.000 claims abstract description 28
- 238000001694 spray drying Methods 0.000 claims abstract description 26
- 239000006184 cosolvent Substances 0.000 claims abstract description 20
- 239000007800 oxidant agent Substances 0.000 claims abstract description 18
- 239000002904 solvent Substances 0.000 claims abstract description 16
- 230000001590 oxidative effect Effects 0.000 claims abstract description 15
- 239000002270 dispersing agent Substances 0.000 claims abstract description 14
- 238000002156 mixing Methods 0.000 claims abstract description 14
- 239000000725 suspension Substances 0.000 claims abstract description 13
- 239000003929 acidic solution Substances 0.000 claims abstract description 12
- 239000006185 dispersion Substances 0.000 claims abstract description 7
- 238000000034 method Methods 0.000 claims description 20
- 229910052799 carbon Inorganic materials 0.000 claims description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 13
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 12
- 229910052751 metal Inorganic materials 0.000 claims description 11
- 239000002184 metal Substances 0.000 claims description 11
- 238000004519 manufacturing process Methods 0.000 claims description 10
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 9
- 239000004743 Polypropylene Substances 0.000 claims description 8
- 238000007906 compression Methods 0.000 claims description 8
- 230000006835 compression Effects 0.000 claims description 8
- 239000012535 impurity Substances 0.000 claims description 8
- 230000002572 peristaltic effect Effects 0.000 claims description 8
- 229920001155 polypropylene Polymers 0.000 claims description 8
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 6
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 6
- 229910017604 nitric acid Inorganic materials 0.000 claims description 6
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 5
- 239000012286 potassium permanganate Substances 0.000 claims description 5
- -1 polypropylene Polymers 0.000 claims description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 3
- 239000004593 Epoxy Substances 0.000 claims 1
- 238000012986 modification Methods 0.000 abstract description 15
- 230000004048 modification Effects 0.000 abstract description 15
- 239000002861 polymer material Substances 0.000 abstract description 13
- 239000002253 acid Substances 0.000 abstract description 9
- 239000000843 powder Substances 0.000 description 13
- 239000000243 solution Substances 0.000 description 13
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 10
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 10
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 10
- 239000002518 antifoaming agent Substances 0.000 description 8
- 230000000694 effects Effects 0.000 description 7
- 239000004576 sand Substances 0.000 description 7
- 238000005469 granulation Methods 0.000 description 6
- 230000003179 granulation Effects 0.000 description 6
- 238000007865 diluting Methods 0.000 description 5
- 239000003822 epoxy resin Substances 0.000 description 5
- 229920003023 plastic Polymers 0.000 description 5
- 239000004033 plastic Substances 0.000 description 5
- 229920000647 polyepoxide Polymers 0.000 description 5
- 239000004594 Masterbatch (MB) Substances 0.000 description 4
- 238000009826 distribution Methods 0.000 description 4
- 230000003647 oxidation Effects 0.000 description 4
- 238000007254 oxidation reaction Methods 0.000 description 4
- 239000003054 catalyst Substances 0.000 description 3
- 125000000524 functional group Chemical group 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 238000005507 spraying Methods 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- WQYVRQLZKVEZGA-UHFFFAOYSA-N hypochlorite Chemical compound Cl[O-] WQYVRQLZKVEZGA-UHFFFAOYSA-N 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 239000002923 metal particle Substances 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- 239000004696 Poly ether ether ketone Substances 0.000 description 1
- JUPQTSLXMOCDHR-UHFFFAOYSA-N benzene-1,4-diol;bis(4-fluorophenyl)methanone Chemical compound OC1=CC=C(O)C=C1.C1=CC(F)=CC=C1C(=O)C1=CC=C(F)C=C1 JUPQTSLXMOCDHR-UHFFFAOYSA-N 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 238000004523 catalytic cracking Methods 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 150000002505 iron Chemical class 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- VUZPPFZMUPKLLV-UHFFFAOYSA-N methane;hydrate Chemical compound C.O VUZPPFZMUPKLLV-UHFFFAOYSA-N 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 229920002530 polyetherether ketone Polymers 0.000 description 1
- 150000003109 potassium Chemical class 0.000 description 1
- 238000009817 primary granulation Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 238000009818 secondary granulation Methods 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
Classifications
-
- 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
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The invention relates to a preparation method of carbon nano tube modified particles, carbon nano tube modified particles and application thereof. The preparation method comprises the following steps: mixing a carbon nano tube, a strong oxidant and an acidic solution to prepare a modified suspension; mixing a solvent, a dispersant, a cosolvent and the modified suspension, and performing dispersion treatment to prepare mixed slurry; spray drying the mixed slurry to prepare the carbon nano tube modified particles; wherein the particle size of the carbon nano tube in the mixed slurry is 100 nm-3 mu m. According to the invention, the strong oxidant, the acid and the carbon nano tube are mixed for preliminary modification, and the mixed slurry with a specific particle size is further prepared, so that the carbon nano tube obtains more surface modification opportunities, the grafting efficiency is greatly improved, more sufficient and effective modification is realized, and the carbon nano tube modified particles prepared by further spray drying can be applied to a high polymer material to remarkably reduce the specific surface resistance and prompt the conductivity resistance of the material.
Description
Technical Field
The invention relates to the field of materials, in particular to a carbon nano tube modified particle and a preparation method and application thereof.
Background
The carbon nanotube, also called buckytubes, is a one-dimensional quantum material with a special structure with the radial dimension of nanometer magnitude and the axial dimension of micrometer magnitude. The carbon nano tube has excellent mechanical property, electrical property, electromagnetic property, optical property, wave-absorbing property and the like, has the potential of being applied to various fields and industries, and has wide development prospect. From the discovery, applications of carbon nanotubes have been related to lithium batteries, plastics, paints, and the like.
The addition of carbon nanotubes in polymeric materials such as plastics can increase surface resistance and improve the antistatic properties of the material. However, in the manufacturing process of the master batch of the polymer material, the direct addition of the carbon nanotube powder easily causes serious dust flying, which causes great harm to operators and mechanical equipment in the production environment, and if a closed space feeding device is adopted, the production line is crowded. Therefore, the granulation of carbon nanotubes is a key point in the application of the carbon nanotubes to the field of plastics and the like, which have a problem of powder scattering.
The existing carbon nanotube granulation process generally comprises the steps of adding carbon nanotubes and water into a wet granulator, mixing, carrying out primary granulation, wherein the process can be understood as compression granulation, then carrying out rolling extrusion in shaping granulation, carrying out secondary granulation, and finally obtaining particles with uniform shapes and particle sizes similar to those of plastic master batches. The method has the disadvantages of low preparation efficiency, poor dispersibility and poor melting property of the prepared carbon nano tube particles in the high polymer material, and the addition amount of the carbon nano tube particles is required to be increased to achieve a better antistatic modification effect, but the original performance of the high polymer material is influenced.
In some researches, hypochlorite and permanganate are used for carrying out primary oxidation treatment on a carbon nano tube under a heating condition, and then hydrogen peroxide solution is added for carrying out secondary oxidation treatment, so that the stability and the dispersibility of the carbon nano tube in the solution are improved, but the method needs to be carried out at 70-80 ℃ and modified through two-step oxidation, the steps are complex, the reaction conditions are not easy to control, and the method is not beneficial to practical production and application, and the modified carbon nano tube prepared by the method is not ideal for improving the antistatic property of the high polymer material when being applied to the high polymer material.
Therefore, it is necessary to provide a method for preparing carbon nanotube particles, which can improve the dispersibility and the melting property of the carbon nanotube particles and the polymer material and further improve the antistatic performance of the material.
Disclosure of Invention
Based on the carbon nanotube modified particle, the invention provides a preparation method of the carbon nanotube modified particle, the carbon nanotube modified particle and application of the carbon nanotube modified particle. The method has good modification effect and simple steps, and the prepared carbon nano tube modified particles and the high polymer material have good dispersibility and meltability, so that the surface resistance of the material can be obviously reduced, and the antistatic property can be improved.
The specific technical scheme is as follows:
in a first aspect of the present invention, there is provided a method for preparing carbon nanotube-modified particles, comprising the steps of:
mixing the carbon nano tube, a strong oxidant and an acidic solution to prepare a modified suspension;
mixing a solvent, a dispersant, a cosolvent and the modified suspension, and performing dispersion treatment to prepare mixed slurry;
spray drying the mixed slurry to prepare the carbon nano tube modified particles;
wherein the particle size of the carbon nano tube in the mixed slurry is 100 nm-3 mu m.
In one embodiment, the strong oxidant is selected from potassium permanganate and hydrogen peroxide.
In one embodiment, the molar ratio of the strong oxidant to the carbon nanotubes is (1.3-2.5): 1.
In one embodiment, the acidic solution is selected from one or more of sulfuric acid, nitric acid, and hydrochloric acid.
In one embodiment, the mass ratio of the acidic solution to the metal impurities in the carbon nanotubes is (1.3-3): 1.
In one embodiment, the mass ratio of the carbon nano tube to the solvent to the dispersant to the cosolvent is (1-7) to (85-97) to (0.5-3) to (0.1-1).
In one embodiment, the solvent is selected from one or more of water and an oily solvent; and/or
The dispersant is selected from PVP; and/or
The cosolvent is one or more selected from NMP, alcohol and acetone.
In one embodiment, the spray drying conditions comprise: the air supply temperature is 100-290 ℃, and the flow rate of the peristaltic pump is 0.1-10L/min; and/or
The compression ratio of spray drying is 1 (5-8).
In a second aspect of the present invention, there is provided carbon nanotube-modified particles produced by the method for producing carbon nanotube-modified particles described above.
In one embodiment, the particle size of the carbon nanotube modified particle is 100 μm to 450 μm.
In a third aspect of the present invention, an application of the carbon nanotube modified particle in a polymer material is provided.
In one embodiment, the polymer material is a polypropylene material or an epoxy resin material.
Compared with the prior art, the invention has the following beneficial effects:
according to the invention, a strong oxidant, acid and the carbon nano tube are mixed for primary modification, and then are further mixed and dispersed with a solvent, a dispersing agent and a cosolvent to prepare a mixed slurry with a specific particle size, so that the carbon nano tube has more opportunities for surface modification, and grafting of functional groups is carried out while dispersion is carried out, thus the grafting efficiency is greatly improved, effective modification is realized, and the carbon nano tube modified particle prepared by further spray drying can significantly reduce the specific surface resistance and improve the conductivity resistance of a high polymer material when being applied to the high polymer material. The method has the advantages of simple preparation steps, easily controlled conditions and obvious modification effect.
In addition, the spray drying method is adopted to achieve the effect of granulation while drying, the process efficiency is greatly improved, and the prepared carbon nano modified particles are uniform and spherical and have high fluidity, thereby providing convenience for subsequent material processing.
Detailed Description
In order that the invention may be more readily understood, reference will now be made to the following more particular description of the invention, examples of which are set forth below. This invention may, however, be embodied in many different forms and should not be construed as limited to the embodiments set forth herein. These embodiments are provided so that this disclosure will be thorough and complete.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used in the description of the invention herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention.
As used herein, the term "and/or", "and/or" includes any and all combinations of two or more of the associated listed items, including any two or any more of the associated listed items, or all of the associated listed items.
In the present invention, "first aspect", "second aspect", "third aspect" and the like are used for descriptive purposes only and are not to be construed as indicating or implying a relative importance or quantity, nor are they to be construed as implicitly indicating the importance or quantity of the technical feature indicated. Moreover, "first," "second," "third," etc. are used merely for purposes of non-exhaustive enumeration and description, and should not be construed as a closed limitation of quantity.
In the present invention, the technical features described in the open type include a closed technical solution including the listed features, and also include an open technical solution including the listed features.
In the present invention, the numerical intervals are regarded as continuous, and include the minimum and maximum values of the range and each value between the minimum and maximum values, unless otherwise specified. Further, when a range refers to an integer, each integer between the minimum and maximum values of the range is included. Further, when multiple range describing features or characteristics are provided, the ranges may be combined. In other words, unless otherwise indicated, all ranges disclosed herein are to be understood to encompass any and all subranges subsumed therein.
The percentage contents referred to in the present invention mean, unless otherwise specified, mass percentages for solid-liquid mixing and solid-liquid mixing, and volume percentages for liquid-liquid mixing.
The temperature parameter in the present invention is not particularly limited, and may be a constant temperature treatment or a treatment within a certain temperature range. The constant temperature process allows the temperature to fluctuate within the accuracy of the instrument control.
The invention provides a preparation method of carbon nano tube modified particles, which comprises the following steps:
mixing the carbon nano tube, a strong oxidant and an acidic solution to prepare a modified suspension;
mixing a solvent, a dispersant, a cosolvent and a modified suspension, and performing dispersion treatment to prepare mixed slurry;
spray drying the mixed slurry to prepare carbon nano tube modified particles;
wherein the particle size of the carbon nano tube in the mixed slurry is 100 nm-3 mu m.
In the invention, a strong oxidant, acid and a carbon nano tube are mixed for preliminary modification, then the mixture is further mixed with a solvent, a dispersant and a cosolvent and dispersed to a specific particle size so as to realize full modification, carboxyl with larger polarity is introduced on the surface of the carbon nano tube through the oxidation of the strong oxidant and the treatment of an acidic solution, so that the surface of the carbon nano tube material has active groups, and then different functional groups are introduced through covalent crosslinking reaction.
In one example, a solvent, a dispersant, a cosolvent, and a modified suspension are mixed in a sand mill, and dispersed to prepare a mixed slurry.
In the invention, a sand mill is adopted for mixing and dispersing to prepare the mixed slurry with a specific particle size, a strong physical dispersing effect can be provided, a large amount of micron-sized aggregates in the carbon nano tubes are opened, more metal particles are exposed, more surface modification opportunities are obtained, and functional groups are grafted while strong dispersion is carried out, so that the grafting efficiency is greatly improved, more sufficient and more effective modification is realized, and the carbon nano tube modified particles prepared by further spray drying are applied to a high polymer material, so that the specific surface resistance of the material can be remarkably reduced, and the conductivity resistance of the material is improved. In addition, the preparation method provided by the invention has simple steps and easily controlled conditions, the spray drying method is adopted to achieve the granulation effect while drying, the process efficiency is greatly improved, the particle size of the prepared carbon nano tube modified particles is uniform, and the purity can reach more than 90%.
In one example, the strong oxidizing agent is selected from potassium permanganate and hydrogen peroxide. It will be appreciated that, in order to facilitate mixing of the materials and sufficient contact modification, a strong oxidant solution may be used in preparing the modified suspension, and the strong oxidant solution may be selected from one of a potassium permanganate solution and a hydrogen peroxide solution. Further, the strong oxidant solution can be one selected from a saturated potassium permanganate solution and a hydrogen peroxide solution with the mass percentage of 30%.
In one example, the molar ratio of the strong oxidant to the carbon nanotubes is (1.3-2.5): 1. Further, the molar ratio of the strong oxidant to the carbon nanotubes includes, but is not limited to: 1.3.
In one example, the acidic solution is selected from one or more of sulfuric acid, nitric acid, and hydrochloric acid.
In one example, the mass ratio of the acidic solution to the metal impurities in the carbon nanotubes is (1.3-3): 1. Further, the quality of the metal impurities in the acidic solution and the carbon nanotubes includes, but is not limited to: 1.3.
In the present invention, the carbon nanotubes are prepared by catalytic cracking with a metal catalyst, and the metal particles are distributed at the tip end and in the middle of the carbon nanotubes, so that the carbon nanotubes contain the metal catalyst, which may also be referred to as metal impurities. It is understood that the content of the metal impurities in the carbon nanotubes can be measured by a conventional measuring method such as ICP, and can also be calculated by calculating the content of the metal catalyst in the carbon nanotubes.
In one example, the mass ratio of the carbon nano tube, the solvent, the dispersant and the cosolvent is (1-7): 85-97): 0.5-3): 0.1-1.
In one example, the solvent is selected from one or more of water and an oily solvent.
In one example, the dispersant is selected from polyvinylpyrrolidone (PVP).
In one example, the co-solvent is selected from one or more of N-methylpyrrolidone (NMP), alcohol, and acetone.
In the present invention, an appropriate amount of an antifoaming agent may be added as necessary.
In one example, the method for preparing the carbon nanotube modified particle further includes the following steps: and diluting the viscosity of the mixed slurry and then performing spray drying. It can be understood that the spray drying can be better performed by diluting the viscosity of the mixed slurry to a specific concentration, and the preparation of the carbon nanotube modified particles with specific particle sizes is facilitated by matching with specific conditions of air supply temperature and peristaltic pump flow.
In one example, the viscosity of the diluted mixed slurry is 1500 to 3500cps.
In one example, the spray drying conditions include: the air supply temperature is 100-290 ℃, and the flow rate of the peristaltic pump is 0.1-10L/min. Further, the temperature of the spray-dried air supply includes, but is not limited to: 100 deg.C, 130 deg.C, 150 deg.C, 170 deg.C, 200 deg.C, 230 deg.C, 250 deg.C, 270 deg.C, 290 deg.C; spray-dried peristaltic pump flow rates include, but are not limited to: 0.1L/min, 0.5L/min, 1L/min, 2L/min, 3L/min, 4L/min, 5L/min, 6L/min, 7L/min, 8L/min, 9L/min, 10L/min.
In one example, the compression ratio of spray drying is 1 (5-8). Further, the compression ratio of spray drying includes but is not limited to 1.
The invention also provides the carbon nano tube modified particle prepared by the preparation method of the carbon nano tube modified particle.
In one example, the particle size of the carbon nanotube-modified particle is 100 μm to 450 μm. Furthermore, the particle size distribution D90 of the carbon nano tube modified particles is 180-340 μm, and the D50 is 106-150 μm.
In the invention, the particle diameter of the prepared carbon nano tube modified particle is kept between 120 and 450 mu m, the particle is uniform and spherical, the spherical characteristic of the particle is different from that of a common carbon nano tube particle, the particle has good fluidity, and the particle can be applied to a special field with fluidity requirements and provides convenience for the subsequent processing of materials.
The invention also provides application of the carbon nano tube modified particle in materials. In one example, the material is a polypropylene material.
The carbon nano tube modified particle provided by the invention has better dispersion performance in the fields of plastics and rubber, and improves the meltability of the carbon nano tube in the material, so that the conductivity of the material modified by adding the carbon nano tube modified particle is more stable. Furthermore, the carbon nano tube modified particle provided by the invention is generally suitable for ABS materials, polypropylene (PP) materials, PEEK materials and some epoxy resin materials, and the mass fraction of the carbon nano tube modified particle added is 0.8-6 percent and can reach 10 percent 3 Ω～10 9 Omega resistance value, and has remarkable antistatic effect.
The present invention will be described in further detail with reference to specific examples. The experimental procedures in the following examples are all conventional ones unless otherwise specified. The raw materials, reagents and the like used in the following examples are all commercially available products unless otherwise specified.
Reagents and apparatus used in the following examples:
carbon nanotube raw powder: jiangxi Yue an New materials GmbH, iron series carbon nano tube raw powder, model YA-E3030;
dispersing agent: PVP;
cosolvent: NMP;
defoaming agent: s1478;
a sand mill: 3L of a sand mill;
spray drying equipment: spray drying with 200kg fluidized bed;
a high-speed stirrer: 2800 rpm high speed stirrer.
Example 1
(1) Adding 1.6L of a 30% hydrogen peroxide solution in mass percent into 100g of carbon nanotube raw powder, adding 1.2L of an acid solution (wherein the mass ratio of concentrated nitric acid to concentrated sulfuric acid is 1: 3), and the mass ratio of the acid solution to metal impurities in the carbon nanotubes (the mass percentage content is 1%) is 1.3;
(2) Adding water, PVP, a cosolvent, a defoaming agent and the modified suspension into a sand mill, and dispersing for 8 hours until the particle size of the carbon nano tube in the mixed slurry is 100 nm-3 mu m; wherein, by mass ratio, water: PVP: defoaming agent: cosolvent: carbon nanotube raw powder = 95.
(3) And (2) placing the mixed slurry in a high-speed stirrer, adding water, stirring and diluting until the viscosity value is 2000cps, spraying the diluted mixed slurry into spray drying equipment, wherein the spray drying conditions are that the air supply temperature is 250 ℃ and the flow rate of a peristaltic pump is 5L/min, so that the carbon nano tube modified particles with specific particle sizes are prepared, the compression ratio is 1.
The initial bulk density of the carbon nanotube raw powder used in this example was 0.01g/ml, and the bulk density of the prepared carbon nanotube-modified particles was 0.08g/ml, and the particle size distribution D90 was 260 μm and D50 was 120 μm. After testing, after the particles are added into PP to prepare master batch, the specific resistance of the particles is 10 when the addition amount is 3.5 percent (mass fraction) 7 Omega, 0.08% by mass of a specific resistance of 10 is added to the epoxy resin E28 8 Ω。
Example 2
(1) Adding 1.6L of a 30% hydrogen peroxide solution in mass percent into 100g of carbon nanotube raw powder, and then adding 1.2L of an acid solution (wherein the mass ratio of concentrated nitric acid to concentrated sulfuric acid is 1: 3), wherein the mass ratio of acid in the acid solution to metal impurities (the mass percentage content is 1%) in the carbon nanotubes is 1.8;
(2) Adding water, PVP, a cosolvent, a defoaming agent and the modified suspension into a sand mill, and dispersing for 6 hours until the particle size of the carbon nano tube in the mixed slurry is 100 nm-3 mu m; wherein, by mass ratio, water: PVP: defoaming agent: cosolvent: carbon nanotube raw powder = 97.
(3) And (2) placing the mixed slurry in a high-speed stirrer, adding water, stirring and diluting until the viscosity value is 2000cps, spraying the diluted mixed slurry into spray drying equipment, wherein the spray drying conditions are that the air supply temperature is 250 ℃ and the flow rate of a peristaltic pump is 5L/min, so that the carbon nano tube modified particles with specific particle sizes are prepared, the compression ratio is 1.
The initial bulk density of the carbon nanotube raw powder used in this example was 0.01g/ml, the bulk density of the processed carbon nanotube particles was 0.06g/ml, and the particle size distribution D90 was 180 μmD50 is 106 μm, and after testing, after adding the particles into PP to prepare master batch, the specific resistance of the particles is 10 when the addition amount is 3.2% (mass fraction) 7 Omega, 0.06% (mass fraction) of specific surface resistance of 10 is added to the epoxy resin E28 8 Ω。
Example 3
(1) Adding 1.6L of hydrogen peroxide solution with the mass percent of 30% into 100g of carbon nanotube raw powder, and then adding 1.2L of acid solution (wherein the mass ratio of concentrated nitric acid to concentrated sulfuric acid is 1;
(2) Adding water, PVP, a cosolvent, a defoaming agent and the modified suspension into a sand mill, and dispersing for 8 hours until the particle size of the carbon nano tube in the mixed slurry is 100 nm-3 mu m; wherein, by mass ratio, water: PVP: defoaming agent: cosolvent: carbon nanotube raw powder = 95.
(3) And (2) placing the mixed slurry in a high-speed stirrer, adding water, stirring and diluting until the viscosity value is 3000cps, spraying the diluted mixed slurry into spray drying equipment, wherein the spray drying conditions are that the air supply temperature is 290 ℃ and the flow rate of a peristaltic pump is 10L/min, and preparing the carbon nano tube modified particles with specific particle sizes, wherein the compression ratio is 1.
The initial bulk density of the carbon nanotube raw powder used in this example was 0.01g/ml, the bulk density of the processed carbon nanotube particles was 0.09g/ml, the particle size distribution D90 was 340 μm, and the D50 was 150 μm, and after the test, the particles were added to PP to prepare a master batch, and the specific resistance of the particles was 10 at an addition level of 3.6% (mass fraction) 7 Omega, 0.08% by mass of a specific resistance of 10 is added to the epoxy resin E28 8 Ω。
All possible combinations of the technical features of the above embodiments may not be described for the sake of brevity, but should be considered as within the scope of the present disclosure as long as there is no contradiction between the combinations of the technical features.
The above-mentioned embodiments only express several embodiments of the present invention, and the description thereof is more specific and detailed, but not construed as limiting the scope of the invention. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the inventive concept, which falls within the scope of the present invention. Therefore, the protection scope of the present patent shall be subject to the appended claims.
Claims (12)
1. A preparation method of carbon nano tube modified particles is characterized by comprising the following steps:
mixing the carbon nano tube, a strong oxidant and an acidic solution to prepare a modified suspension;
mixing a solvent, a dispersant, a cosolvent and the modified suspension, and performing dispersion treatment to prepare mixed slurry;
spray drying the mixed slurry to prepare the carbon nano tube modified particles;
wherein the particle size of the carbon nano tube in the mixed slurry is 100 nm-3 mu m.
2. The method for preparing carbon nanotube modified particles according to claim 1, wherein the strong oxidizing agent is one selected from potassium permanganate and hydrogen peroxide.
3. The method for producing carbon nanotube-modified particles according to claim 2, wherein the molar ratio of the strong oxidizing agent to the carbon nanotubes is (1.3 to 2.5): 1.
4. The method of claim 1, wherein the acidic solution is one or more selected from the group consisting of sulfuric acid, nitric acid, and hydrochloric acid.
5. The method of producing carbon nanotube-modified particles according to claim 4, wherein the mass ratio of the acidic solution to the metal impurities in the carbon nanotubes is (1.3-3): 1.
6. The method for producing carbon nanotube-modified particles according to claim 1, wherein the mass ratio of the carbon nanotube to the solvent to the dispersant to the co-solvent is (1-7): (85-97): (0.5-3): (0.1-1).
7. The method for producing carbon nanotube-modified particles according to any one of claims 1 to 6, wherein the solvent is one or more selected from the group consisting of water and an oily solvent; and/or
The dispersant is selected from PVP; and/or
The cosolvent is one or more selected from NMP, alcohol and acetone.
8. The method for producing carbon nanotube-modified particles according to any one of claims 1 to 6, wherein the conditions for spray-drying include: the air supply temperature is 100-290 ℃, and the flow of the peristaltic pump is 0.1-10L/min; and/or
The compression ratio of spray drying is 1 (5-8).
9. The carbon nanotube-modified particle produced by the method for producing carbon nanotube-modified particle according to any one of claims 1 to 8.
10. The carbon nanotube-modified particle according to claim 9, wherein the particle diameter of the carbon nanotube-modified particle is 100 to 450 μm.
11. Use of the carbon nanotube-modified particle of any one of claims 9 to 10 in a polymeric material.
12. Use according to claim 11, wherein the polymeric material is a polypropylene material or an epoxy material.
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