CN110218377B - Preparation method of multi-walled carbon nanotube/copper sulfide composite electromagnetic shielding film - Google Patents
Preparation method of multi-walled carbon nanotube/copper sulfide composite electromagnetic shielding film Download PDFInfo
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- CN110218377B CN110218377B CN201910536240.6A CN201910536240A CN110218377B CN 110218377 B CN110218377 B CN 110218377B CN 201910536240 A CN201910536240 A CN 201910536240A CN 110218377 B CN110218377 B CN 110218377B
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- walled carbon
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- 239000002048 multi walled nanotube Substances 0.000 title claims abstract description 120
- 239000002131 composite material Substances 0.000 title claims abstract description 47
- OMZSGWSJDCOLKM-UHFFFAOYSA-N copper(II) sulfide Chemical compound [S-2].[Cu+2] OMZSGWSJDCOLKM-UHFFFAOYSA-N 0.000 title claims abstract description 46
- 238000002360 preparation method Methods 0.000 title claims abstract description 26
- 239000003431 cross linking reagent Substances 0.000 claims abstract description 60
- 229920002873 Polyethylenimine Polymers 0.000 claims abstract description 59
- 239000007864 aqueous solution Substances 0.000 claims abstract description 40
- 229920000459 Nitrile rubber Polymers 0.000 claims abstract description 33
- 239000000243 solution Substances 0.000 claims abstract description 32
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims abstract description 22
- 239000000839 emulsion Substances 0.000 claims abstract description 14
- AKHNMLFCWUSKQB-UHFFFAOYSA-L sodium thiosulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=S AKHNMLFCWUSKQB-UHFFFAOYSA-L 0.000 claims abstract description 14
- 235000019345 sodium thiosulphate Nutrition 0.000 claims abstract description 14
- 238000010438 heat treatment Methods 0.000 claims abstract description 12
- 238000002156 mixing Methods 0.000 claims abstract description 12
- 238000005266 casting Methods 0.000 claims description 30
- 239000011521 glass Substances 0.000 claims description 30
- 239000011259 mixed solution Substances 0.000 claims description 27
- 239000007788 liquid Substances 0.000 claims description 20
- 229920000642 polymer Polymers 0.000 claims description 20
- 239000007787 solid Substances 0.000 claims description 20
- 238000003756 stirring Methods 0.000 claims description 20
- 229920000126 latex Polymers 0.000 claims description 19
- 239000004816 latex Substances 0.000 claims description 19
- 150000002825 nitriles Chemical class 0.000 claims description 18
- JZCCFEFSEZPSOG-UHFFFAOYSA-L copper(II) sulfate pentahydrate Chemical compound O.O.O.O.O.[Cu+2].[O-]S([O-])(=O)=O JZCCFEFSEZPSOG-UHFFFAOYSA-L 0.000 claims description 12
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 11
- 229910000366 copper(II) sulfate Inorganic materials 0.000 claims description 10
- 238000001035 drying Methods 0.000 claims description 10
- 238000007790 scraping Methods 0.000 claims description 10
- 238000002791 soaking Methods 0.000 claims description 10
- 238000009210 therapy by ultrasound Methods 0.000 claims description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- XNINAOUGJUYOQX-UHFFFAOYSA-N 2-cyanobutanoic acid Chemical compound CCC(C#N)C(O)=O XNINAOUGJUYOQX-UHFFFAOYSA-N 0.000 claims description 2
- 229910000365 copper sulfate Inorganic materials 0.000 abstract description 8
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 abstract description 8
- 239000000463 material Substances 0.000 abstract description 8
- 239000011159 matrix material Substances 0.000 abstract description 5
- 238000000034 method Methods 0.000 abstract description 5
- 239000012528 membrane Substances 0.000 abstract description 4
- 238000010521 absorption reaction Methods 0.000 abstract description 2
- 239000007888 film coating Substances 0.000 abstract description 2
- 238000009501 film coating Methods 0.000 abstract description 2
- 239000000203 mixture Substances 0.000 abstract description 2
- 239000000126 substance Substances 0.000 abstract description 2
- 238000006243 chemical reaction Methods 0.000 description 8
- 239000000945 filler Substances 0.000 description 7
- 238000011049 filling Methods 0.000 description 5
- 238000011161 development Methods 0.000 description 4
- 230000005670 electromagnetic radiation Effects 0.000 description 4
- NOWKCMXCCJGMRR-UHFFFAOYSA-N Aziridine Chemical compound C1CN1 NOWKCMXCCJGMRR-UHFFFAOYSA-N 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 3
- 238000004891 communication Methods 0.000 description 3
- 229910001431 copper ion Inorganic materials 0.000 description 3
- 229920001971 elastomer Polymers 0.000 description 3
- 239000005060 rubber Substances 0.000 description 3
- IZAHANVODSCYKP-UHFFFAOYSA-N C=CC#N.OC(=O)C=CC=C Chemical compound C=CC#N.OC(=O)C=CC=C IZAHANVODSCYKP-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000002041 carbon nanotube Substances 0.000 description 2
- 229910021393 carbon nanotube Inorganic materials 0.000 description 2
- 230000000536 complexating effect Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 1
- NTXGQCSETZTARF-UHFFFAOYSA-N buta-1,3-diene;prop-2-enenitrile Chemical compound C=CC=C.C=CC#N NTXGQCSETZTARF-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 210000000748 cardiovascular system Anatomy 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000010668 complexation reaction Methods 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- BWFPGXWASODCHM-UHFFFAOYSA-N copper monosulfide Chemical class [Cu]=S BWFPGXWASODCHM-UHFFFAOYSA-N 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 125000004093 cyano group Chemical group *C#N 0.000 description 1
- 210000000750 endocrine system Anatomy 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 229920001002 functional polymer Polymers 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 210000000987 immune system Anatomy 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000012212 insulator Substances 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 210000000653 nervous system Anatomy 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000003014 reinforcing effect Effects 0.000 description 1
- 210000004994 reproductive system Anatomy 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K9/00—Screening of apparatus or components against electric or magnetic fields
- H05K9/0073—Shielding materials
- H05K9/0081—Electromagnetic shielding materials, e.g. EMI, RFI shielding
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2313/00—Characterised by the use of rubbers containing carboxyl groups
-
- 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
- C08K3/30—Sulfur-, selenium- or tellurium-containing compounds
- C08K2003/3009—Sulfides
-
- 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
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
-
- 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
- C08K3/041—Carbon nanotubes
Abstract
The invention relates to the technical field of functional material preparation, in particular to a preparation method of a multi-walled carbon nanotube/copper sulfide composite electromagnetic shielding film. Firstly, mixing a multi-walled carbon nanotube, a carboxyl nitrile rubber emulsion and a polyaziridine cross-linking agent solution, immersing the mixture into a solution containing copper sulfate for curing after film coating, adding a sodium thiosulfate aqueous solution into the copper sulfate solution after forming, heating, and reacting by adopting a chemical bath method to generate copper sulfide, thereby finally obtaining the multi-walled carbon nanotube/copper sulfide composite electromagnetic shielding film. The copper sulfate prepared by the method not only grows on the surface of the nitrile rubber, but also grows and polymerizes in the nitrile rubber, so that the formed copper sulfate can cover the surface of a nitrile rubber matrix membrane and also penetrates into the membrane, the effective absorption of copper sulfide is really completed, and the composite material has excellent electromagnetic shielding performance.
Description
Technical Field
The invention relates to the technical field of functional material preparation, in particular to a preparation method of a multi-walled carbon nanotube/copper sulfide composite electromagnetic shielding film.
Background
With the rapid development of the electronic industry and the increasing popularity of various commercial and household communication devices and electronic products, the electromagnetic wave radiation generated by these products is filled with electromagnetic waves with different wavelengths and frequencies, so that the electromagnetic radiation pollution is more and more serious. Electromagnetic radiation not only can interfere communication equipment such as radio and television, but also can affect human health, and a nervous system, a cardiovascular system, an endocrine system, a reproductive system, an immune system and the like can be damaged to different degrees when a human body is exposed to the electromagnetic radiation environment for a long time. Electromagnetic radiation pollution has attracted attention from various countries in the world, and a series of standards and regulations for shielding electromagnetic waves are established in succession by many countries and international organizations, such as FCC regulation of the federal communications commission in the united states, VDE regulation of the german electrical technology association, CISPR international standard of the international electrical standards committee, and the like.
The polymer has the characteristics of corrosion resistance, light weight, excellent mechanics, easy processing and the like, so the polymer has wider application in the production and the life of people. With the rapid development of energy, electronics and other fields in recent years, people have increasingly demanded polymer materials with functional characteristics such as electric conduction and heat conduction. However, except that a few polymers have electrical conductivity, most polymers are electrical and thermal insulators, and the polymers cannot meet the requirement of multifunctionality, so that the development of polymer composite materials with the functions of electrical conductivity, thermal conductivity, electromagnetic shielding and the like is an important subject in front of researchers. The functional polymer composite material prepared by filling the functional nano filler has the advantages of low cost, short development period, easy popularization and the like, and is widely concerned at home and abroad.
The electromagnetic shielding material can be classified into a coating type structure type, a filling type and the like, and the filling type shielding material is a composite material consisting of a polymer matrix filler and other additives. The metal-based shielding material and the carbon-based shielding material can be classified according to the additive. The functional nano-filler not only can provide multifunctional characteristics for the polymer, but also has a certain reinforcing effect on the polymer, however, the pure addition of the nano-filler generally needs very high filling amount, which is not beneficial to the processing and forming of the composite material, and meanwhile, most of the nano-fillers have rigidity, which can greatly reduce the toughness of the composite material. For the increasingly improved requirements of thinness, lightness, width and strength required by the electromagnetic shielding technology, one material is difficult to meet the comprehensive requirement, so that the optimal electromagnetic wave absorbing performance is achieved by compounding various types of powder according to the specific requirement.
Disclosure of Invention
In order to solve the technical problems, the invention provides a preparation method of a multi-walled carbon nanotube/copper sulfide composite electromagnetic shielding film, and the material obtained by adopting the method has good electromagnetic shielding performance and flexibility.
The technical scheme of the invention is realized as follows:
a preparation method of a multi-walled carbon nanotube/copper sulfide composite electromagnetic shielding film comprises the following steps:
(1) adding the multi-walled carbon nanotube into a polyethylenimine cross-linking agent aqueous solution, stirring and mixing, and then carrying out ultrasonic treatment for 60-120min to uniformly disperse the multi-walled carbon nanotube to obtain a multi-walled carbon nanotube/polyethylenimine cross-linking agent mixed solution;
(2) adding the multi-walled carbon nanotube/polyethylenimine crosslinking agent mixed solution prepared in the step (1) into a carboxyl nitrile rubber emulsion, stirring for 2-3h at the temperature of 60-80 ℃ to obtain a multi-walled carbon nanotube/polyethylenimine crosslinking agent/carboxyl nitrile rubber mixed solution, standing and defoaming to prepare a polymer casting solution;
(3) and (3) casting the casting solution obtained in the step (2) on a glass plate, scraping the glass plate into a liquid film with the thickness of 600-1200 microns by using a scraper, immersing the glass plate with the liquid film into a blue vitriol aqueous solution, soaking for 1-4 hours at the temperature of 10-40 ℃, adding a sodium thiosulfate aqueous solution, heating to the temperature of 75-95 ℃, reacting for 0.5-4 hours, taking out the blended film, rinsing with water, and drying to obtain the multi-walled carbon nanotube/copper sulfide composite electromagnetic shielding film.
The mass ratio of the multi-walled carbon nanotube to the polyethylenimine crosslinking agent aqueous solution in the step (1) is (1-5): (95-99).
The multi-walled carbon nanotube is one of a carboxylated multi-walled carbon nanotube or an aminated multi-walled carbon nanotube, and the mass concentration of the polyaziridine cross-linking agent aqueous solution is 40-80%.
The amino content of the aminated multi-wall carbon nanotube is 0.45 percent, the diameter is 10-15nm, the length is 50 mu m, the carboxyl content of the carboxylated multi-wall carbon nanotube is 1.23 percent, the diameter is 20-30nm, and the length is 20 mu m; the model of the polyethylenimine crosslinking agent is XR-100, and the solid content is more than or equal to 99 percent.
The dosage of the multi-wall carbon nano tube/polyethylenimine crosslinking agent mixed solution in the step (2) is 5-15% of the mass of the carboxylated nitrile-butadiene rubber emulsion.
The carboxyl butyronitrile latex has the model number of FM301, the solid content of 41 +/-1 percent and the content of bound nitrile of more than or equal to 30 percent.
The mass concentration of the copper sulfate pentahydrate aqueous solution in the step (3) is 2-10 percent; the mass concentration of the sodium thiosulfate aqueous solution is 2-10%.
The invention has the beneficial effects that:
(1) firstly, mixing a multi-walled carbon nanotube, a carboxyl nitrile rubber emulsion and a polyaziridine cross-linking agent solution, immersing the mixture into a solution containing copper sulfate for curing after film coating, adding a sodium thiosulfate aqueous solution into the copper sulfate solution after forming, heating, and reacting by adopting a chemical bath method to generate copper sulfide, thereby finally obtaining the multi-walled carbon nanotube/copper sulfide composite electromagnetic shielding film. The copper sulfate prepared by the method not only grows on the surface of the nitrile rubber, but also grows and polymerizes in the nitrile rubber, so that the formed copper sulfate can cover the surface of a nitrile rubber matrix membrane and also penetrates into the membrane, the effective absorption of copper sulfide is really completed, and the composite material has excellent electromagnetic shielding performance.
(2) The trifunctional aziridine used in the invention has larger tension and higher activity in structure, and a large number of groups exist in molecules, so that the trifunctional aziridine can react with carboxyl, amino and hydroxyl at normal temperature to generate an insoluble cross-linked product with a network structure. This patent make full use of aziridine molecule not only can take place the reaction with carboxyl butadiene-acrylonitrile rubber molecule but also can take place the characteristics of complexation with copper ion to it forms butadiene-acrylonitrile rubber molecule and electrically conductive copper sulfide as the cross-linking agent and alternates each other, makes copper sulfide distribute in carboxyl butadiene-acrylonitrile rubber network uniformly, has improved the electric conductive property of electrically conductive complex film. The multi-wall carbon nano-tubes and the copper sulfide particles are different types of fillers, and are mutually dispersed in gaps in a carboxylic acrylonitrile butadiene rubber latex matrix, so that the filling factor of the fillers can be increased, more conductive path networks are formed in the carboxylic acrylonitrile butadiene rubber matrix, the resistance is reduced, and the composite material with better electromagnetic shielding performance is obtained.
(3) The cyano in the carboxyl nitrile rubber has a complexing effect on copper ions, and due to the introduction of the strong chelating adsorption effect of the polyethylenimine crosslinking agent, a large number of amino N atoms are arranged on a macromolecular chain of the carboxyl nitrile rubber, so that the carboxyl nitrile rubber has strong electron accepting performance, the carboxyl nitrile rubber can generate a strong complexing effect on the copper ions, the loading capacity of copper sulfides on a carboxyl nitrile rubber film is improved, and the electromagnetic shielding performance and durability of a flexible film are effectively improved.
(4) The preparation method has the advantages of easily controlled conditions, simple operation, low raw material cost and low energy consumption, and is suitable for large-scale industrial production.
Detailed Description
The technical solutions of the present invention will be described clearly and completely with reference to the following embodiments of the present invention, and it should be understood that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be obtained by a person skilled in the art without inventive effort based on the embodiments of the present invention, are within the scope of the present invention.
Example 1
The preparation method of the multiwalled carbon nanotube/copper sulfide composite electromagnetic shielding film comprises the following steps:
(1) adding 0.8 g of carboxylated multi-wall carbon nano tube into 9.2 g of 70% polyaziridine cross-linking agent aqueous solution, stirring and mixing, and then carrying out ultrasonic treatment for 70min to uniformly disperse the multi-wall carbon nano tube to obtain a multi-wall carbon nano tube/polyaziridine cross-linking agent mixed solution;
(2) adding 1.1 g of the carboxylated multi-wall carbon nanotube/polyethylenimine crosslinking agent mixed solution prepared in the step (1) into 10 g of nitrile rubber emulsion, stirring at 75 ℃ for 2.5h to obtain a carboxylated multi-wall carbon nanotube/polyethylenimine crosslinking agent/carboxylated nitrile rubber latex mixed solution, and standing for defoaming to obtain a polymer casting solution;
(3) and (3) casting the casting solution obtained in the step (2) onto a glass plate, scraping the glass plate into a liquid film with the thickness of 950 microns by using a scraper, immersing the glass plate with the liquid film into 50 g of 6% aqueous solution of blue vitriol, soaking at 23 ℃ for 2.5 hours, adding 50 g of 6% aqueous solution of sodium thiosulfate, heating to 85 ℃ for reaction for 2 hours, taking out the blended film, rinsing with water, and drying to obtain the multi-walled carbon nanotube/copper sulfide composite electromagnetic shielding film. The multi-walled carbon nanotube/copper sulfide composite electromagnetic shielding film has the shielding effectiveness of 38dB in the range of 80MHz-6 GHz.
The type of the carboxylated nitrile latex used in the embodiment is FM301, the solid content is 41 +/-1 percent, and the content of the combined nitrile is more than or equal to 30 percent; the type of the used polyethylenimine crosslinking agent is XR-100, and the solid content is more than or equal to 99 percent; the content of amino in the used aminated multi-wall carbon nano-tube is 0.45 percent, the diameter is 10-15nm, and the length is 50 mu m; the carboxyl content of the used carboxylated multi-wall carbon nano-tube is 1.23 percent, the diameter is 20-30nm, and the length is 20 mu m.
Example 2
The preparation method of the multiwalled carbon nanotube/copper sulfide composite electromagnetic shielding film comprises the following steps:
(1) adding 0.5 g of carboxylated multi-wall carbon nano tube into 9.5 g of an 80% polyaziridine cross-linking agent aqueous solution, stirring, mixing, and performing ultrasonic treatment for 120min to uniformly disperse the multi-wall carbon nano tube to obtain a carboxylated multi-wall carbon nano tube/polyaziridine cross-linking agent mixed solution;
(2) adding 0.5 g of the multi-wall carbon nanotube/polyethylenimine crosslinking agent mixed solution prepared in the step (1) into 10 g of nitrile-butadiene rubber emulsion, stirring at 80 ℃ for 2h to obtain a multi-wall carbon nanotube/polyethylenimine crosslinking agent/carboxylated nitrile-butadiene latex blended solution, standing and defoaming to obtain a polymer casting solution;
(3) and (3) casting the casting solution obtained in the step (2) onto a glass plate, scraping the glass plate into a liquid film with the thickness of 600 microns by using a scraper, immersing the glass plate with the liquid film into 50 g of a 5% aqueous solution of blue vitriol, soaking at 10 ℃ for 4 hours, adding 50 g of a 5% aqueous solution of sodium thiosulfate, heating to 95 ℃ for reaction for 0.5 hour, taking out the blended film, rinsing with water, and drying to obtain the carbon nano tube/copper sulfide composite electromagnetic shielding film. The multi-walled carbon nanotube/copper sulfide composite electromagnetic shielding film has the shielding effectiveness of 38dB in the range of 80MHz-6 GHz.
The type of the carboxylated nitrile latex used in the embodiment is FM301, the solid content is 41 +/-1 percent, and the content of the combined nitrile is more than or equal to 30 percent; the type of the used polyethylenimine crosslinking agent is XR-100, and the solid content is more than or equal to 99 percent; the content of amino in the used aminated multi-wall carbon nano-tube is 0.45 percent, the diameter is 10-15nm, and the length is 50 mu m; the carboxyl content of the used carboxylated multi-wall carbon nano-tube is 1.23 percent, the diameter is 20-30nm, and the length is 20 mu m.
Example 3
The preparation method of the multiwalled carbon nanotube/copper sulfide composite electromagnetic shielding film comprises the following steps:
(1) adding 0.1 g of aminated multi-walled carbon nanotubes into 9.9 g of 30% polyethylenimine crosslinking agent aqueous solution, stirring and mixing, and then carrying out ultrasonic treatment for 60min to uniformly disperse the aminated multi-walled carbon nanotubes to obtain a multi-walled carbon nanotube/polyethylenimine crosslinking agent mixed solution;
(2) adding 1.5 g of the aminated multi-walled carbon nanotube/polyethylenimine crosslinking agent mixed solution prepared in the step (1) into 10 g of nitrile-butadiene rubber emulsion, stirring for 3h at 60 ℃ to obtain an aminated multi-walled carbon nanotube/polyethylenimine crosslinking agent/carboxylated nitrile-butadiene latex blended solution, and standing for defoaming to obtain a polymer casting solution;
(3) and (3) casting the casting solution obtained in the step (2) onto a glass plate, scraping the glass plate into a liquid film with the thickness of 700 microns by using a scraper, immersing the glass plate with the liquid film into 50 g of 2% aqueous solution of blue vitriol, soaking at 40 ℃ for 1 hour, adding 50 g of 2% aqueous solution of sodium thiosulfate, heating to 75 ℃ for reaction for 4 hours, taking out the blended film, rinsing with water, and drying to obtain the carbon nano tube/copper sulfide composite electromagnetic shielding film. The multi-walled carbon nanotube/copper sulfide composite electromagnetic shielding film has the shielding effectiveness of 27dB in the range of 80MHz-6 GHz.
The type of the carboxylated nitrile latex used in the embodiment is FM301, the solid content is 41 +/-1 percent, and the content of the combined nitrile is more than or equal to 30 percent; the type of the used polyethylenimine crosslinking agent is XR-100, and the solid content is more than or equal to 99 percent; the content of amino in the used aminated multi-wall carbon nano-tube is 0.45 percent, the diameter is 10-15nm, and the length is 50 mu m; the carboxyl content of the used carboxylated multi-wall carbon nano-tube is 1.23 percent, the diameter is 20-30nm, and the length is 20 mu m.
Example 4
The preparation method of the multiwalled carbon nanotube/copper sulfide composite electromagnetic shielding film comprises the following steps:
(1) adding 0.4 g of aminated multi-walled carbon nanotubes into 9.6 g of a 50% polyethylenimine crosslinking agent aqueous solution, stirring and mixing, and then carrying out ultrasonic treatment for 110min to uniformly disperse the aminated multi-walled carbon nanotubes to obtain a multi-walled carbon nanotube/polyethylenimine crosslinking agent mixed solution;
(2) adding 1.4 g of the aminated multi-walled carbon nanotube/polyethylenimine crosslinking agent mixed solution prepared in the step (1) into 10 g of nitrile-butadiene rubber emulsion, stirring at 70 ℃ for 2.5h to obtain an aminated multi-walled carbon nanotube/polyethylenimine crosslinking agent/carboxylated nitrile-butadiene latex blended solution, and standing for defoaming to obtain a polymer casting solution;
(3) and (3) casting the casting solution obtained in the step (2) onto a glass plate, scraping the glass plate into a liquid film with the thickness of 1200 microns by using a scraper, immersing the glass plate with the liquid film into 50 g of a 5% aqueous solution of blue vitriol, soaking at 30 ℃ for 2 hours, adding 50 g of a 5% aqueous solution of sodium thiosulfate, heating to 85 ℃ for reaction for 2 hours, taking out the blended film, rinsing with water, and drying to obtain the multi-walled carbon nanotube/copper sulfide composite electromagnetic shielding film. The multi-walled carbon nanotube/copper sulfide composite electromagnetic shielding film has the shielding effectiveness of 54dB in the range of 80MHz-6 GHz.
The type of the carboxylated nitrile latex used in the embodiment is FM301, the solid content is 41 +/-1 percent, and the content of the combined nitrile is more than or equal to 30 percent; the type of the used polyethylenimine crosslinking agent is XR-100, and the solid content is more than or equal to 99 percent; the content of amino in the used aminated multi-wall carbon nano-tube is 0.45 percent, the diameter is 10-15nm, and the length is 50 mu m; the carboxyl content of the used carboxylated multi-wall carbon nano-tube is 1.23 percent, the diameter is 20-30nm, and the length is 20 mu m.
Example 5
The preparation method of the multiwalled carbon nanotube/copper sulfide composite electromagnetic shielding film comprises the following steps:
(1) adding 0.3 g of carboxylated multi-walled carbon nanotubes into 9.7 g of a 50% polyethylenimine crosslinking agent aqueous solution, stirring, mixing, and then carrying out ultrasonic treatment for 100min to uniformly disperse the carboxylated multi-walled carbon nanotubes to obtain a carboxylated multi-walled carbon nanotube/polyethylenimine crosslinking agent mixed solution;
(2) adding 0.8 g of the carboxylated multi-wall carbon nanotube/polyethylenimine crosslinking agent mixed solution prepared in the step (1) into 10 g of nitrile rubber emulsion, stirring at 65 ℃ for 2.5h to obtain a carboxylated multi-wall carbon nanotube/polyethylenimine crosslinking agent/carboxylated nitrile rubber latex mixed solution, and standing for defoaming to obtain a polymer casting solution;
(3) and (3) casting the casting solution obtained in the step (2) onto a glass plate, scraping the glass plate into a liquid film with the thickness of 900 micrometers by using a scraper, immersing the glass plate with the liquid film into 50 g of 8% aqueous solution of blue vitriol, soaking at 35 ℃ for 2 hours, adding 50 g of 8% aqueous solution of sodium thiosulfate, heating to 90 ℃ for reaction for 1 hour, taking out the blended film, rinsing with water, and drying to obtain the multi-walled carbon nanotube/copper sulfide composite electromagnetic shielding film. The multi-walled carbon nanotube/copper sulfide composite electromagnetic shielding film has the shielding effectiveness of 48dB within the range of 80MHz-6 GHz.
The type of the carboxylated nitrile latex used in the embodiment is FM301, the solid content is 41 +/-1 percent, and the content of the combined nitrile is more than or equal to 30 percent; the type of the used polyethylenimine crosslinking agent is XR-100, and the solid content is more than or equal to 99 percent; the content of amino in the used aminated multi-wall carbon nano-tube is 0.45 percent, the diameter is 10-15nm, and the length is 50 mu m; the carboxyl content of the used carboxylated multi-wall carbon nano-tube is 1.23 percent, the diameter is 20-30nm, and the length is 20 mu m.
Example 6
The preparation method of the multiwalled carbon nanotube/copper sulfide composite electromagnetic shielding film comprises the following steps:
(1) adding 0.2 g of aminated multi-walled carbon nanotube into 9.8 g of 65% polyethylenimine crosslinking agent aqueous solution, stirring and mixing, and then carrying out ultrasonic treatment for 90min to uniformly disperse the aminated multi-walled carbon nanotube so as to obtain an aminated multi-walled carbon nanotube/polyethylenimine crosslinking agent mixed solution;
(2) adding 0.6 g of the aminated multi-walled carbon nanotube/polyethylenimine crosslinking agent mixed solution prepared in the step (1) into 10 g of nitrile-butadiene rubber emulsion, stirring at 75 ℃ for 2.5h to obtain an aminated multi-walled carbon nanotube/polyethylenimine crosslinking agent/carboxylated nitrile-butadiene latex mixed solution, and standing for defoaming to obtain a polymer casting solution;
(3) and (3) casting the casting solution obtained in the step (2) onto a glass plate, scraping the glass plate into a liquid film with the thickness of 1100 microns by using a scraper, immersing the glass plate with the liquid film into 50 g of 3% aqueous solution of blue vitriol, soaking for 3 hours at 25 ℃, adding 50 g of 3% aqueous solution of sodium thiosulfate, heating to 80 ℃, reacting for 1.5 hours, taking out the blended film, rinsing with water, and drying to obtain the multi-walled carbon nanotube/copper sulfide composite electromagnetic shielding film. The multi-walled carbon nanotube/copper sulfide composite electromagnetic shielding film has the shielding effectiveness of 23dB in the range of 80MHz-6 GHz.
The type of the carboxylated nitrile latex used in the embodiment is FM301, the solid content is 41 +/-1 percent, and the content of the combined nitrile is more than or equal to 30 percent; the type of the used polyethylenimine crosslinking agent is XR-100, and the solid content is more than or equal to 99 percent; the content of amino in the used aminated multi-wall carbon nano-tube is 0.45 percent, the diameter is 10-15nm, and the length is 50 mu m; the carboxyl content of the used carboxylated multi-wall carbon nano-tube is 1.23 percent, the diameter is 20-30nm, and the length is 20 mu m.
Example 7
The preparation method of the multiwalled carbon nanotube/copper sulfide composite electromagnetic shielding film comprises the following steps:
(1) adding 0.4 g of carboxylated multi-walled carbon nanotubes into 9.6 g of an 80% polyethylenimine crosslinking agent aqueous solution, stirring, mixing, and then carrying out ultrasonic treatment for 80min to uniformly disperse the carboxylated multi-walled carbon nanotubes to obtain a carboxylated multi-walled carbon nanotube/polyethylenimine crosslinking agent mixed solution;
(2) adding 1.5 g of the carboxylated multi-wall carbon nanotube/polyethylenimine crosslinking agent mixed solution prepared in the step (1) into 10 g of nitrile rubber emulsion, stirring at 75 ℃ for 2h to obtain a carboxylated multi-wall carbon nanotube/polyethylenimine crosslinking agent/carboxylated nitrile rubber latex blended solution, and standing for defoaming to obtain a polymer casting solution;
(3) and (3) casting the casting solution obtained in the step (2) onto a glass plate, scraping the glass plate into a liquid film with the thickness of 1000 microns by using a scraper, immersing the glass plate with the liquid film into 50 g of a 4% aqueous solution of blue vitriol, soaking at 28 ℃ for 2 hours, adding 50 g of a 4% aqueous solution of sodium thiosulfate, heating to 82 ℃ for reaction for 1.5 hours, taking out the blended film, rinsing with water, and drying to obtain the multi-walled carbon nanotube/copper sulfide composite electromagnetic shielding film. The multi-walled carbon nanotube/copper sulfide composite electromagnetic shielding film has the shielding effectiveness of 45dB within the range of 80MHz-6 GHz.
The type of the carboxylated nitrile latex used in the embodiment is FM301, the solid content is 41 +/-1 percent, and the content of the combined nitrile is more than or equal to 30 percent; the type of the used polyethylenimine crosslinking agent is XR-100, and the solid content is more than or equal to 99 percent; the content of amino in the used aminated multi-wall carbon nano-tube is 0.45 percent, the diameter is 10-15nm, and the length is 50 mu m; the carboxyl content of the used carboxylated multi-wall carbon nano-tube is 1.23 percent, the diameter is 20-30nm, and the length is 20 mu m.
Example 8
The preparation method of the multiwalled carbon nanotube/copper sulfide composite electromagnetic shielding film comprises the following steps:
(1) adding 0.45 g of aminated multi-walled carbon nanotubes into 9.55 g of 65% polyethylenimine cross-linking agent aqueous solution, stirring and mixing, and then carrying out ultrasonic treatment for 70min to uniformly disperse the multi-aminated multi-walled carbon nanotubes so as to obtain an aminated multi-walled carbon nanotube/polyethylenimine cross-linking agent mixed solution;
(2) adding 1.3 g of the aminated multi-walled carbon nanotube/polyethylenimine crosslinking agent mixed solution prepared in the step (1) into 10 g of nitrile-butadiene rubber emulsion, stirring at 65 ℃ for 2.5h to obtain an aminated multi-walled carbon nanotube/polyethylenimine crosslinking agent/carboxylated nitrile-butadiene latex blended solution, and standing for defoaming to obtain a polymer casting solution;
(3) and (3) casting the casting solution obtained in the step (2) onto a glass plate, scraping the glass plate into a liquid film with the thickness of 900 microns by using a scraper, immersing the glass plate with the liquid film into 50 g of 10% aqueous solution of blue vitriol, soaking at 25 ℃ for 2.5 hours, adding 50 g of 10% aqueous solution of sodium thiosulfate, heating to 88 ℃ for reaction for 1.5 hours, taking out the blended film, rinsing with water, and drying to obtain the multi-walled carbon nanotube/copper sulfide composite electromagnetic shielding film. The multi-walled carbon nanotube/copper sulfide composite electromagnetic shielding film has the shielding effectiveness of 53dB in the range of 80MHz-6 GHz.
The type of the carboxylated nitrile latex used in the embodiment is FM301, the solid content is 41 +/-1 percent, and the content of the combined nitrile is more than or equal to 30 percent; the type of the used polyethylenimine crosslinking agent is XR-100, and the solid content is more than or equal to 99 percent; the content of amino in the used aminated multi-wall carbon nano-tube is 0.45 percent, the diameter is 10-15nm, and the length is 50 mu m; the carboxyl content of the used carboxylated multi-wall carbon nano-tube is 1.23 percent, the diameter is 20-30nm, and the length is 20 mu m.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents, improvements and the like that fall within the spirit and principle of the present invention are intended to be included therein.
Claims (5)
1. A preparation method of a multi-wall carbon nanotube/copper sulfide composite electromagnetic shielding film is characterized by comprising the following steps:
(1) adding the multi-walled carbon nanotube into a polyethylenimine cross-linking agent aqueous solution, stirring and mixing, and then carrying out ultrasonic treatment for 60-120min to uniformly disperse the multi-walled carbon nanotube to obtain a multi-walled carbon nanotube/polyethylenimine cross-linking agent mixed solution;
(2) adding the multi-walled carbon nanotube/polyethylenimine crosslinking agent mixed solution prepared in the step (1) into a carboxyl nitrile rubber emulsion, stirring for 2-3h at the temperature of 60-80 ℃ to obtain a multi-walled carbon nanotube/polyethylenimine crosslinking agent/carboxyl nitrile rubber mixed solution, standing and defoaming to prepare a polymer casting solution;
(3) casting the polymer casting solution obtained in the step (2) on a glass plate, scraping the glass plate into a liquid film with the thickness of 600-1200 microns by using a scraper, immersing the glass plate with the liquid film into a blue vitriol aqueous solution, soaking for 1-4 hours at the temperature of 10-40 ℃, adding a sodium thiosulfate aqueous solution, heating to the temperature of 75-95 ℃, reacting for 0.5-4 hours, taking out the blended film, rinsing with water, and drying to obtain the multi-walled carbon nanotube/copper sulfide composite electromagnetic shielding film;
the mass ratio of the multi-walled carbon nanotube to the polyethylenimine crosslinking agent aqueous solution in the step (1) is (1-5): (95-99); the mass concentration of the polyaziridine cross-linking agent aqueous solution is 40-80%;
the dosage of the multi-wall carbon nano tube/polyethylenimine crosslinking agent mixed solution in the step (2) is 5-15% of the mass of the carboxylated nitrile-butadiene rubber emulsion.
2. The preparation method of the multi-walled carbon nanotube/copper sulfide composite electromagnetic shielding film according to claim 1, wherein the preparation method comprises the following steps: the multi-walled carbon nanotube is one of a carboxylated multi-walled carbon nanotube or an aminated multi-walled carbon nanotube.
3. The preparation method of the multi-walled carbon nanotube/copper sulfide composite electromagnetic shielding film according to claim 2, wherein the preparation method comprises the following steps: the amino content of the aminated multi-wall carbon nanotube is 0.45 percent, the diameter is 10-15nm, the length is 50 mu m, the carboxyl content of the carboxylated multi-wall carbon nanotube is 1.23 percent, the diameter is 20-30nm, and the length is 20 mu m; the model of the polyethylenimine crosslinking agent is XR-100, and the solid content is more than or equal to 99 percent.
4. The preparation method of the multi-walled carbon nanotube/copper sulfide composite electromagnetic shielding film according to claim 3, wherein the preparation method comprises the following steps: the carboxyl butyronitrile latex has the model number of FM301, the solid content of 41 +/-1 percent and the content of bound nitrile of more than or equal to 30 percent.
5. The preparation method of the multi-walled carbon nanotube/copper sulfide composite electromagnetic shielding film according to claim 1, wherein the preparation method comprises the following steps: the mass concentration of the copper sulfate pentahydrate aqueous solution in the step (3) is 2-10 percent; the mass concentration of the sodium thiosulfate aqueous solution is 2-10%.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2000013090A (en) * | 1998-06-23 | 2000-01-14 | Jamco Corp | Gasket |
| CN105131359A (en) * | 2015-09-19 | 2015-12-09 | 四川大学 | Graphene/carbon nano tube hybridized filler network enhanced rubber material and preparation method thereof |
| CN107557769A (en) * | 2017-07-26 | 2018-01-09 | 昆明理工大学 | A kind of preparation method of complex metal layer coating carbon nanotubes electromagnetic shielding material |
| CN109898107A (en) * | 2019-02-28 | 2019-06-18 | 昆明理工大学 | Foam metal Copper-cladding Aluminum Bar carbon nano tube electromagnetic shielding material and preparation method |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20070275237A1 (en) * | 2006-05-24 | 2007-11-29 | Syh-Tau Yeh | Electromagnetic shielding tape |
-
2019
- 2019-06-20 CN CN201910536240.6A patent/CN110218377B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2000013090A (en) * | 1998-06-23 | 2000-01-14 | Jamco Corp | Gasket |
| CN105131359A (en) * | 2015-09-19 | 2015-12-09 | 四川大学 | Graphene/carbon nano tube hybridized filler network enhanced rubber material and preparation method thereof |
| CN107557769A (en) * | 2017-07-26 | 2018-01-09 | 昆明理工大学 | A kind of preparation method of complex metal layer coating carbon nanotubes electromagnetic shielding material |
| CN109898107A (en) * | 2019-02-28 | 2019-06-18 | 昆明理工大学 | Foam metal Copper-cladding Aluminum Bar carbon nano tube electromagnetic shielding material and preparation method |
Non-Patent Citations (1)
| Title |
|---|
| 硫化体系对导电炭黑填充NBR 胶料性能的影响;曾敏 等;《橡胶工业》;20091231;第56卷(第7期);第406-411页 * |
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