CN115652650A - Flexible electromagnetic shielding PVC composite film and preparation method thereof - Google Patents
Flexible electromagnetic shielding PVC composite film and preparation method thereof Download PDFInfo
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Abstract
The invention provides a preparation method of a flexible electromagnetic shielding PVC composite film, which is characterized in that a polymer/hydrotalcite-like single-layer nano material is used for modifying a hydroxyl carbon nanotube and ferroferric oxide respectively, on one hand, hydrotalcite-like modification not only improves the dispersion of the hydroxyl carbon nanotube and the ferroferric oxide in a PVC matrix, but also improves the compatibility of the hydroxyl carbon nanotube and the ferroferric oxide with PVC; on the other hand, the introduction of hydrotalcite-like compound is beneficial to improving the dielectric loss of the composite film. The hydrotalcite-like modified hydroxyl carbon nanotube, ferroferric oxide and PVC are compounded, so that the conductivity, the magnetic property and the dielectric property of the PVC are obviously improved, and the PVC material has good electromagnetic shielding property. The invention also provides a flexible electromagnetic shielding PVC composite film.
Description
[ technical field ] A
The invention relates to the technical field of nano materials, in particular to a flexible electromagnetic shielding PVC composite film and a preparation method thereof.
[ background of the invention ]
With the wide application of electronic communication technology in various fields, the pollution of electromagnetic radiation generated thereby is increased, and therefore, there is a need to develop a high-performance electromagnetic interference (EMI) shielding material to suppress or reduce the interference of electromagnetic radiation on electronic components and human health threats. The polymer-based electromagnetic shielding composite material is a polymer material with a conductive function, which is formed by uniformly dispersing a functional filler (such as a conductive filler, a magnetic filler and the like) in a one-phase or multi-phase polymer matrix through different processing modes (melting, solution or other forming methods). However, the existing polymer-based electromagnetic shielding composite material has the defects of low conductivity, poorer electromagnetic shielding performance than a metal material and the like. How to improve the electromagnetic shielding performance through the structural design becomes a key scientific and technical problem which needs to be solved urgently. In addition, the conductive filler such as carbon nano tube and the magnetic filler such as ferroferric oxide are easy to agglomerate when being blended with the polymer due to small-size effect and surface effect, so that the conductive filler is unevenly distributed, and the improvement of the electromagnetic shielding performance is influenced. Therefore, it is necessary to provide a flexible electromagnetic shielding PVC composite film and a method for preparing the same to solve the above problems.
[ summary of the invention ]
The invention aims to provide a flexible electromagnetic shielding PVC composite film and a preparation method thereof, which can solve the technical problems related to the background technology.
The technical scheme of the invention is as follows:
a preparation method of a flexible electromagnetic shielding PVC composite film comprises the following steps:
s10: ultrasonically dispersing the polymer/hydrotalcite-like single-layer nano material into water, and uniformly dispersing to obtain a polymer/hydrotalcite-like single-layer nano turbid liquid;
s20: ultrasonically dispersing a hydroxyl carbon nanotube into water, and uniformly dispersing to obtain a hydroxyl carbon nanotube solution; mixing the polymer/hydrotalcite-like single-layer nano turbid liquid with the hydroxyl carbon nanotube solution, generating a precipitate immediately under the action of electrostatic self-assembly, and centrifuging, washing with water, washing with methanol and drying the precipitate to obtain a modified carbon nanotube composite material;
s30: adding the polymer/hydrotalcite-like single-layer nano-suspension into a solution for preparing ferroferric oxide by adopting a coprecipitation method, and slowly dropwise adding 40mL of NH 3 ·H 2 O, crystallizing at the temperature of 80 ℃ for 1 hour, centrifuging the slurry obtained by crystallization to obtain a precipitate, and respectively centrifuging and washing the precipitate for 5-10 times by using ethanol and water to obtain a modified ferroferric oxide nano composite material;
s40: putting 15-20% of PVC, 6-10% of modified carbon nanotube composite material, 6-10% of modified ferroferric oxide nanocomposite material, 2-6% of pore-forming agent and 54-71% of solvent into a 250ml three-neck flask according to the mass percentage, heating, stirring, dissolving and mixing at 70 ℃, and fully defoaming to obtain a polymer solution; and scraping the polymer solution on the surface of the non-woven fabric into a flat membrane at the speed of 0.1-5.0m/s at room temperature, cooling by air, solidifying and forming in water at room temperature, soaking for 12-24h to remove the solvent and the pore-forming agent, taking out and drying to obtain the flexible electromagnetic shielding PVC composite membrane with the membrane thickness of 0.8-1.5mm.
Preferably, in step S10, the preparation process of the "polymer/hydrotalcite-like single-layer nanomaterial" is as follows:
s11: dispersing a polymer A containing carboxyl or carboxylic anhydride groups into an aqueous solution, and adding an excessive alkali solution for treatment to obtain a polymer ion salt solution;
s12: dissolving divalent metal ion salt and trivalent metal ion salt in water to obtain mixed metal ion salt solution;
s13: dropwise adding the mixed metal ion salt solution into the polymer salt solution at a certain temperature under the protection of inert gas, and adjusting the pH value in the reaction process by using an alkali solution to ensure that the pH value of the system is not more than 10;
s14: and (4) centrifuging the slurry obtained after the reaction in the step (S13) is finished, and centrifuging and washing the precipitate to be neutral by using ethanol and water respectively to obtain the polymer/hydrotalcite-like single-layer nano material.
Preferably, the divalent metal ion in the divalent metal ion salt is Mg 2+ The trivalent metal ion in the trivalent metal ion salt is Al 3+ The anion in the mixed metal ion salt solution is NO 3- The molar ratio of the divalent metal ions to the trivalent metal ions is (2-5): 1; the mass ratio of the trivalent metal ion salt to the polymer A is 1 (1-10); the polymer A is one of polyacrylic acid, ethylene acrylic acid copolymer and polystyrene/carboxylic anhydride functional group copolymer; the reaction temperature in the step S13 is 60-80 ℃, the inert gas is nitrogen or argon, the reaction time is 6-24h, and the alkali solution is ammonia water, a sodium hydroxide solution or a potassium hydroxide solution.
Preferably, in the step S20, the concentration ratio of the polymer/hydrotalcite-like single-layer nanomaterial suspension to the concentration of the hydroxyl carbon nanotube solution mixture is (1.
Preferably, in the step S30, the preparation process of the "solution for preparing ferroferric oxide by using a coprecipitation method" includes: 0.06mol of FeCl 3 ·6H 2 O and 0.03mol of FeSO 4 ·7H H 2 Adding O into a three-neck flask containing a certain volume of deionized water, and performing ultrasonic treatment for 5min to dissolve the O.
Preferably, in the step S30, the volume ratio of the polymer/hydrotalcite-like compound monolayer nano-suspension to the solution for preparing ferroferric oxide by a coprecipitation method is 1-1.
Preferably, in step S40, the pore-forming agent is polyethylene glycol, and the molecular weight is one of 200g/mol, 400g/mol, 600g/mol, 800g/mol, and 1000 g/mol; the solvent is one of N, N-dimethylformamide, N-dimethylacetamide, N-methylpyrrolidone and dimethyl sulfoxide; the non-woven fabric is polyethylene terephthalate or polyamide non-woven fabric, and the thickness of the non-woven fabric is 50-150 mu m.
The invention also provides a flexible electromagnetic shielding PVC composite film prepared by the preparation method.
Compared with the prior art, the polymer/hydrotalcite-like single-layer nano material is used for respectively modifying the hydroxyl carbon nano tube and the ferroferric oxide, so that the surface energy of the carbon nano tube and the magnetic response strength of the ferroferric oxide are reduced, and the agglomeration of the carbon nano tube and the ferroferric oxide in a polymer matrix is relieved; after modification, on one hand, the acting force between the carbon nano tube and the ferroferric oxide and PVC can be improved, the problem that the carbon nano tube and the ferroferric oxide are easy to fall off in a PVC matrix is solved, more interfaces can be obtained, interface polarization is generated, the absorption of electromagnetic waves is favorably improved, and the electromagnetic shielding performance is further improved; on the other hand, the introduced hydrotalcite-like compound is beneficial to improving the dielectric loss of the PVC composite film, thereby further improving the electromagnetic shielding performance. In the process of preparing the PVC composite membrane, the dispersity and compatibility of the carbon nano tube and the ferroferric oxide in a polymer matrix are further improved by utilizing the entanglement between a PVC chain and a polymer chain segment connecting the carbon nano tube and the ferroferric oxide after membrane forming. The hydrotalcite-like modified hydroxyl carbon nanotube, ferroferric oxide and PVC are compounded, so that the conductivity, magnetic property and dielectric property of the PVC are obviously improved, and the PVC material has good electromagnetic shielding property.
[ description of the drawings ]
In order to more clearly illustrate the technical solutions in the embodiments of the present invention, the drawings needed to be used in the description of the embodiments are briefly introduced below, it is obvious that the drawings in the following description are only some embodiments of the present invention, and other drawings can be obtained by those skilled in the art without inventive efforts, wherein:
fig. 1 is an XRD spectrum of the modified carbon nanotube composite in example 1;
FIG. 2 is an SEM photograph of a modified carbon nanotube composite of example 1;
FIG. 3 is a diagram showing a state in which a modified carbon nanocomposite material in example 1 is dispersed in a solvent;
FIG. 4 is an XDR map of the modified ferroferric oxide nanocomposite material in example 1;
FIG. 5 is an infrared spectrum of the modified ferroferric oxide nanocomposite material in example 1;
FIG. 6 is an SEM photograph of a modified ferroferric oxide nanocomposite material in example 1;
FIG. 7 is an EDX diagram of a modified ferroferric oxide nanocomposite material in example 1;
FIG. 8 is a diagram of a dispersion state of a modified ferroferric oxide nanocomposite in a solvent in example 1;
FIG. 9 is a cross-sectional view of the flexible electromagnetic shielding PVC composite film prepared in example 1;
FIG. 10 is a sectional view of a PVC composite film obtained in a comparative example.
[ detailed description ] embodiments
In order to make the technical solutions in the embodiments of the present invention better understood and make the above objects, features and advantages of the present invention more comprehensible, specific embodiments of the present invention are described below with reference to the accompanying drawings of the present application.
Referring to fig. 1 to 10, the present invention provides a method for preparing a flexible electromagnetic shielding PVC composite film, comprising the following steps:
s10: and ultrasonically dispersing the polymer/hydrotalcite-like single-layer nano material into water, and uniformly dispersing to obtain a polymer/hydrotalcite-like single-layer nano turbid liquid.
The preparation process of the polymer/hydrotalcite-like single-layer nano material comprises the following steps:
s11: dispersing a polymer A containing carboxyl or carboxylic anhydride groups into an aqueous solution, and adding an excessive alkali solution for treatment to obtain a polymer ion salt solution;
s12: dissolving divalent metal ion salt and trivalent metal ion salt in water to obtain mixed metal ion salt solution;
s13: dropwise adding the mixed metal ion salt solution into the polymer salt solution at a certain temperature under the protection of inert gas, and adjusting the pH value in the reaction process by using an alkali solution to ensure that the pH value of the system is not more than 10;
s14: and (4) centrifuging the slurry obtained after the reaction in the step (S13) is finished, and centrifuging and washing the precipitate to be neutral by using ethanol and water respectively to obtain the polymer/hydrotalcite-like single-layer nano material.
The polymer A is one of polyacrylic acid, ethylene acrylic acid copolymer and polystyrene/carboxylic anhydride functional group copolymer. The divalent metal ion in the divalent metal ion salt is Mg 2+ The trivalent metal ion in the trivalent metal ion salt is Al 3+ The anion in the mixed metal ion salt solution is NO 3- The molar ratio of the divalent metal ions to the trivalent metal ions is (2-5) to 1; the mass ratio of the trivalent metal ion salt to the polymer A is 1 (1-10). The divalent metal ion of the present invention is a divalent metal ion capable of forming a hydroxide, and is not limited to Mg 2+ (ii) a Similarly, the trivalent metal ion in the present invention is a trivalent metal ion capable of generating a hydroxide, and is not limited to Al only 3+ 。
The polymer A containing carboxyl or carboxylic anhydride groups reacts with an alkaline solution to obtain a carboxylate radical-containing polymer salt aqueous solution, on one hand, the carboxylate radical-containing polymer salt aqueous solution serves as interlayer anions in coprecipitation and is directly combined with the surface of hydrotalcite, and on the other hand, the polymer A also serves as a laminate inhibitor in the coprecipitation reaction process to inhibit growth and assembly of the laminate inhibitor in the (003) direction, so that the high-dispersion polymer/hydrotalcite-like single-layer nano material is prepared. The polymer/hydrotalcite-like single-layer nano material is successfully prepared in water solution by one step through a traditional coprecipitation method, and can be dispersed in water, thereby laying a foundation for wider application of the polymer/hydrotalcite-like single-layer nano material.
Specifically, the reaction temperature in the step S13 is 60-80 ℃, the inert gas is nitrogen or argon, the reaction time is 6-24h, and the alkali solution is ammonia, sodium hydroxide solution or potassium hydroxide solution.
S20: ultrasonically dispersing a hydroxyl carbon nanotube into water, uniformly dispersing to obtain a hydroxyl carbon nanotube solution, mixing the polymer/hydrotalcite-like single-layer nano turbid liquid and the hydroxyl carbon nanotube solution, generating a precipitate immediately under the action of electrostatic self-assembly, and centrifuging, washing with water, washing with methanol and drying the precipitate to obtain the modified carbon nanotube composite material.
S30: adding the polymer/hydrotalcite-like single-layer nano-suspension into a solution for preparing ferroferric oxide by adopting a coprecipitation method, and slowly dropwise adding 40mL of NH 3 ·H 2 And O, crystallizing at the temperature of 80 ℃ for 1 hour, centrifuging the slurry obtained by crystallization to obtain a precipitate, and respectively centrifuging and washing the precipitate for 5-10 times by using ethanol and water to obtain the modified ferroferric oxide nanocomposite.
The polymer/hydrotalcite-like single-layer nanometer turbid liquid carries positive charges, the hydroxyl carbon nanotube solution carries negative charges, and after the polymer/hydrotalcite-like single-layer nanometer turbid liquid and the hydroxyl carbon nanotube solution are mixed, the modified carbon nanometer composite material can be obtained in a static self-assembly mode between two types of nanometer particles, so that the surface energy of the carbon nanotube is reduced, and the problem of agglomeration of the carbon nanotube in a polymer matrix is solved.
After modification, on one hand, the acting force between the carbon nano tube and the ferroferric oxide and subsequent PVC can be improved, the problem that the carbon nano tube and the ferroferric oxide are easy to fall off in a PVC matrix is solved, more interfaces can be obtained to generate interface polarization, the absorption of electromagnetic waves is favorably improved, and the electromagnetic shielding performance is further improved; on the other hand, the introduced hydrotalcite-like compound is beneficial to improving the dielectric loss of the PVC composite film, thereby further improving the electromagnetic shielding performance.
The concentration ratio of the polymer/hydrotalcite-like single-layer nano material suspension to the hydroxyl carbon nanotube solution is (1.
In the step S30, the preparation process of the "preparation of the solution of ferroferric oxide by the coprecipitation method" includes: 0.06mol of FeCl 3 ·6H 2 O and 0.03mol of FeSO 4 ·7H H 2 Adding O into a three-neck flask containing a certain volume of deionized water, and performing ultrasonic treatment for 5min to dissolve the O. In the step S30, the volume ratio of the polymer/hydrotalcite-like single-layer nano-suspension to the solution for preparing ferroferric oxide by a coprecipitation method is 1 to 1, and the total volume is 100ml.
S30: subjecting the polymer to a polymerization reactionAdding hydrotalcite-like single-layer nano turbid liquid into solution for preparing ferroferric oxide by adopting coprecipitation method, and slowly dropwise adding 40mL NH 3 ·H 2 And O, crystallizing at the temperature of 80 ℃ for 1 hour, centrifuging the slurry obtained by crystallization to obtain a precipitate, and respectively centrifuging and washing the precipitate for 5-10 times by using ethanol and water respectively to obtain the hydrotalcite-like modified ferroferric oxide nanocomposite.
S40: putting 15-20% of PVC, 6-10% of modified carbon nanotube composite material, 6-10% of modified ferroferric oxide nanocomposite material, 2-6% of pore-forming agent and 54-71% of solvent into a 250ml three-neck flask according to the mass percentage, heating, stirring, dissolving and mixing at 70 ℃, and fully defoaming to obtain a polymer solution; and scraping the polymer solution on the surface of the non-woven fabric into a flat membrane at the speed of 0.1-5.0m/s at room temperature, cooling by air, solidifying and forming in water at room temperature, soaking for 12-24h to remove the solvent and the pore-forming agent, taking out and drying to obtain the flexible electromagnetic shielding PVC composite membrane with the membrane thickness of 0.8-1.5mm.
In the step S40, the pore-foaming agent is polyethylene glycol, and the molecular weight is one of 200g/mol, 400g/mol, 600g/mol, 800g/mol and 1000 g/mol; the solvent is one of N, N-dimethylformamide, N-dimethylacetamide, N-methylpyrrolidone and dimethyl sulfoxide; the non-woven fabric is polyethylene terephthalate or polyamide non-woven fabric, and the thickness of the non-woven fabric is 50-150 mu m.
The invention also provides a flexible electromagnetic shielding PVC composite film prepared by the preparation method.
In the process of preparing the PVC composite membrane, the entanglement between the PVC chain and the polymer chain segment connected with the carbon nano tube after the membrane is formed is utilized, so that the dispersibility and the compatibility of the carbon nano tube in a polymer matrix are further improved, the composite material can be uniformly dispersed in the polymer, and the better conductivity and mechanical property are obtained. Modified carbon nanotubes, example 1
The embodiment provides a preparation method of a flexible electromagnetic shielding PVC composite film, which comprises the following steps:
(1) Taking 0.025mol of Mg (NO) 3 ) 2 ·6H 2 O and 0.0125mol of Al (NO) 3 ) 3 ·9H 2 Pouring O into the A1 beaker, and adding 50ml of deionized water for dissolving; pouring polyacrylic acid into 200ml B1 flask, and adding Al (NO) 3 ) 3 ·9H 2 The mass ratio of O to polyacrylic acid is 1; pouring 50ml of deionized water into a B1 three-neck flask, and adding excessive ammonia water to perform ring opening reaction to obtain a polyacrylate solution; adding a magnetic stirrer, inserting a pH meter into a B1 three-neck flask, adjusting the temperature in the B1 three-neck flask to 60 ℃, adjusting the rotating speed of the magnetic stirrer to 500 revolutions per minute, then respectively dropwise adding the solution in the A1 flask into the B1 three-neck flask for reaction, adjusting the pH value in the reaction process by using ammonia water, supplementing the ammonia water when the pH value is less than 10 to keep the pH value of the system at about 10 all the time, and protecting by nitrogen in the process. Stirring for 6h after the dripping is finished; then putting the product into a centrifuge tube, and centrifuging for 5min at the rotating speed of 10000 rpm; and removing the supernatant to obtain a precipitate, washing the precipitate with ethanol and deionized water respectively, and centrifuging at 10000rpm for 3min. Dispersing the obtained product into 200ml of deionized water by ultrasonic dispersion to obtain uniformly dispersed polymer/hydrotalcite-like single-layer nano turbid liquid.
(2) Ultrasonically dispersing a hydroxyl carbon nano tube into water, and uniformly dispersing to obtain a hydroxyl carbon nano tube solution; and (3) mixing the polymer/hydrotalcite-like single-layer nano suspension and the hydroxyl carbon nanotube solution in an equal volume according to the concentration ratio of 1.
Referring to fig. 1, fig. 1 is an XRD pattern of the modified carbon nanotube composite material of example 1, and it can be seen from fig. 1 that characteristic diffraction peaks of hydrotalcite-like compounds, which correspond to characteristic peaks of hydrotalcite-like compounds (003), (006), (009), (015), (018), (110) and (113), respectively, occur near 2 θ =5 °, 11.6 °, 22.8 °, 34.6 °, 45.9 ° and 60.4 °/61.6 °, and strong carbon peaks occur at 29.5 °, indicating successful preparation of the modified carbon nanotube nanocomposite material.
Referring to fig. 2, fig. 2 is an SEM image of the modified carbon nanotube composite material of example 1, and it can be seen from fig. 2 that hydrotalcite-like platelets and carbon nanotubes are stacked one on top of the other and interlaced together to form a porous structure.
Referring to fig. 3, fig. 3 is a diagram illustrating a dispersion state of the modified carbon nanotube nanocomposite in the solvent in example 1, and it can be seen from fig. 3 that the modified carbon nanotube nanocomposite can be uniformly and stably dispersed in the solvent, and a tyndall phenomenon occurs, indicating that the modified carbon nanotube nanocomposite has good dispersibility in the solvent.
(3) 50ml of polymer/hydrotalcite-like single-layer nano suspension containing 0.06mol of FeCl 3 ·6H 2 O and 0.03mol of FeSO 4 ·7H H 2 And (2) in the mixed solution of O, the volume ratio of the two is 1.
Referring to fig. 4, fig. 4 is an XDR map of the modified ferriferrous oxide nanocomposite in example 1, and as can be seen from fig. 4, 2theta =18.3 °, 30.1 °, 35.4 °, 37 °, 43.0 °, and 53.4 ° belong to characteristic peaks of ferriferrous oxide, and a hydrotalcite-like typical (110) characteristic diffraction peak exists at about 62 °, which indicates that the modified ferriferrous oxide nanocomposite is successfully prepared.
Referring to FIG. 5, FIG. 5 is an infrared spectrum of the modified ferroferric oxide nanocomposite material obtained in example 1, and it can be seen from FIG. 5 that 3500cm -1 The accessory has a hydroxyl stretching vibration peak; 3000cm -1 The vibration peak of C-H is nearby; 1544cm -1 And 1408cm -1 Is the stretching vibration peak of carboxyl; 1495cm -1 And 1454cm -1 Is the vibration of the benzene ring; 1650cm -1 The bending deformation vibration of interlayer water molecules is nearby; 1000cm -1 The vibration peaks of different metal bonds M-O-M on the laminate further prove the success of the preparation of the modified ferroferric oxide nano composite material.
Referring to fig. 6, fig. 6 is an SEM image of the modified ferriferrous oxide nanocomposite material in example 1, and it can be seen from fig. 6 that the ferriferrous oxide growing in an array is present on the surface of the hydrotalcite-like compound to wrap the hydrotalcite-like compound.
Referring to fig. 7 and table 1, fig. 7 is an EDX diagram of the modified ferroferric oxide nanocomposite in example 1, table 1 shows the content of surface elements of the modified ferroferric oxide nanocomposite in example 1, and it can be seen from fig. 7 and table 1 that the surface iron and oxygen content of the modified ferroferric oxide nanocomposite is high, which further proves the success of the preparation of the modified ferroferric oxide nanocomposite.
TABLE 1 surface element content of modified ferroferric oxide nanocomposite
Referring to fig. 8, fig. 8 is a diagram of a dispersion state of the modified ferroferric oxide nanocomposite in the solvent in example 1, and it can be seen from fig. 7 that the modified ferroferric oxide nanocomposite can be uniformly and stably dispersed in the solvent, and a tyndall phenomenon occurs, indicating that the modified ferroferric oxide nanocomposite has good dispersion performance in the solvent.
(4) Putting 15 percent of PVC, 10 percent of modified carbon nanotube composite material, 10 percent of modified ferroferric oxide nanocomposite material, 6 percent of polyethylene glycol with the molecular weight of 100g/mol and 59 percent of N, N-dimethylformamide into a 250ml three-neck flask, heating, stirring, dissolving and mixing at 70 ℃, and fully defoaming to obtain a casting solution; and scraping the casting solution on the surface of the polyethylene terephthalate non-woven fabric at the speed of 0.1m/s into a flat membrane at room temperature, cooling by air, solidifying and forming in room-temperature water, soaking for 12 hours to remove polyethylene glycol and N, N-dimethylformamide, taking out and drying to obtain the flexible electromagnetic shielding PVC composite membrane with the thickness of 1.5mm.
Referring to fig. 9, fig. 9 is a cross-sectional view of the flexible electromagnetic shielding PVC composite film prepared in example 1, and it can be seen from fig. 9 that the modified carbon nanotubes and ferroferric oxide are uniformly dispersed in the PVC matrix, and have good compatibility with the PVC matrix without delamination.
Example 2
The embodiment provides a preparation method of a flexible electromagnetic shielding PVC composite film, which comprises the following steps:
(1) 0.0375mol of Mg (NO) is taken 3 ) 2 ·6H 2 O, 0.0125mol of Al (NO) 3 ) 3 ·9H 2 Pouring O into the A1 beaker, and adding 50ml of deionized water for dissolving; pouring polystyrene/N-phenylmaleimide/carboxylic anhydride functional terpolymer into 200ml B1 three-neck flask, adding Al (NO) 3 ) 3 The mass ratio of the 9H2O to the polystyrene/N-phenylmaleimide/carboxylic anhydride functional group terpolymer is 1; adding a magnetic stirrer, inserting a pH meter into a B1 three-neck flask, adjusting the temperature in the B1 three-neck flask to 80 ℃, adjusting the rotation speed of the magnetic stirrer to 500 revolutions per minute, then respectively dropwise adding the solution in the A1 flask into the B1 three-neck flask for reaction, adjusting the pH value in the reaction process by using a sodium hydroxide solution, and supplementing the sodium hydroxide solution when the pH value is less than 10 so as to keep the pH value of the system at about 10 all the time, wherein nitrogen is used for protection in the process. Stirring for 18h after the dripping is finished; then putting the product into a centrifuge tube, and centrifuging for 5min at the rotating speed of 10000 rpm; removing supernatant to obtain precipitate, washing the precipitate with ethanol and deionized water, and centrifuging at 10000rpm for 3min. Dispersing the obtained product into 200ml of deionized water by ultrasonic dispersion to obtain uniformly dispersed polymer/hydrotalcite-like single-layer nano turbid liquid;
(2) Ultrasonically dispersing a hydroxyl carbon nanotube into water, and uniformly dispersing to obtain a hydroxyl carbon nanotube solution; mixing the polymer/hydrotalcite-like single-layer nanometer suspension and the hydroxyl carbon nanotube solution in an equal volume according to the concentration ratio of 1;
(3) 75ml of polymer/hydrotalcite-like single-layer nano suspension containing 0.06mol of FeCl 3 ·6H 2 O and 0.03mol of FeSO 4 ·7H H 2 In the mixed solution of O, the volume ratio of the two is 1;
(4) Putting 18 percent of PVC, 8 percent of modified carbon nanotube composite material, 6 percent of modified ferroferric oxide nanocomposite material, 2 percent of polyethylene glycol with the molecular weight of 600g/mol and 66 percent of N, N-dimethylacetamide into a 250ml three-neck flask, heating, stirring, dissolving and mixing at 70 ℃, and fully defoaming to obtain a casting solution; and scraping the casting solution on the surface of the polyethylene terephthalate non-woven fabric at the speed of 3.5m/s into a flat membrane at room temperature, cooling by air, solidifying and forming in room-temperature water, soaking for 18 hours to remove polyethylene glycol and N, N-dimethylacetamide, taking out, and drying to obtain the flexible electromagnetic shielding PVC composite membrane with the thickness of 1.0mm.
Example 3
The embodiment provides a preparation method of a flexible electromagnetic shielding PVC composite film, which comprises the following steps:
(1) Taking 0.0625mol of Mg (NO) 3 ) 2 ·6H 2 O, 0.0125mol of Al (NO) 3 ) 3 ·9H 2 Pouring O into the A1 beaker, and adding 50ml of deionized water for dissolving; pouring the polyacrylonitrile/styrene-butadiene rubber/carboxylic anhydride functional group terpolymer into a 200ml B1 three-neck flask, and adding Al (NO) 3 ) 3 ·9H 2 The mass ratio of the O to the polyacrylonitrile/styrene-butadiene rubber/carboxylic anhydride functional group terpolymer is 1; adding magnetic stirring bar, inserting pH meter into B1 three-neck flask, adjusting temperature in B1 three-neck flask to 90 deg.C, adjusting rotation speed of magnetic stirring bar to 500 r/min, dropwise adding the solution in A1 flask into B1 three-neck flask for reaction, and adding potassium hydroxideThe solution adjusts the pH value in the reaction process, if the pH value is less than 10, the potassium hydroxide solution is supplemented to keep the pH value of the system at about 10 all the time, and nitrogen protection is provided in the process. Stirring for 24h after the dripping is finished; then putting the product into a centrifuge tube, and centrifuging for 5min at the rotating speed of 10000 rpm; and removing the supernatant to obtain a precipitate, washing the precipitate with ethanol and deionized water respectively, and centrifuging at 10000rpm for 3min. Dispersing the obtained product into 200ml of deionized water by ultrasonic dispersion to obtain a uniformly dispersed polymer/hydrotalcite-like single-layer nano turbid liquid;
(2) Ultrasonically dispersing a hydroxyl carbon nanotube into water, and uniformly dispersing to obtain a hydroxyl carbon nanotube solution; mixing the polymer/hydrotalcite-like single-layer nanometer suspension and the hydroxyl carbon nanotube solution in an equal volume according to the concentration ratio of 20;
(3) The volume of the polymer/hydrotalcite-like single-layer nano suspension liquid is 83ml, and the suspension liquid contains 0.06mol of FeCl 3 ·6H 2 O and 0.03mol of FeSO 4 ·7H H 2 In the mixed solution of O, the volume ratio of the two is 1;
(4) Putting 20 percent of PVC, 6 percent of modified carbon nano tube composite material, 6 percent of modified ferroferric oxide nano composite material, 2 percent of polyethylene glycol with the molecular weight of 1000g/mol and 66 percent of dimethyl sulfoxide into a 250ml three-neck flask, heating, stirring, dissolving and mixing at 70 ℃, and fully defoaming to obtain a casting solution; and scraping the casting solution on the surface of the polyethylene terephthalate non-woven fabric at the speed of 5.0m/s into a flat membrane at room temperature, cooling by air, solidifying and forming in room-temperature water, soaking for 24 hours to remove polyethylene glycol and dimethyl sulfoxide, taking out, and drying to obtain the flexible electromagnetic shielding PVC composite membrane with the membrane thickness of 1.5mm.
Comparative example
Putting 15% of PVC, 10% of carbon nano tube, 10% of ferroferric oxide, 6% of polyethylene glycol with the molecular weight of 100g/mol and 5m9% of N, putting N-dimethylformamide into a 250ml three-neck flask, heating, stirring and dissolving at 70 ℃, mixing, and fully defoaming to obtain a polymer solution; and scraping the polymer solution on the surface of the polyamide non-woven fabric at the speed of 0.1m/s into a flat membrane at room temperature, cooling by air, solidifying and forming in room-temperature water, soaking for 12 hours to remove polyethylene glycol and dimethylformamide, taking out, and drying to obtain the PVC composite membrane with the thickness of 1.5mm.
Referring to fig. 10, fig. 10 is a cross-sectional view of a PVC composite film obtained by a comparative example, and comparing fig. 9 and fig. 10, it can be seen that the distribution of ferroferric oxide and carbon nanotubes in fig. 10 is not uniform enough, and a certain degree of delamination occurs.
The flexible electromagnetic shielding PVC composite film prepared in the examples 1 to 3 and the PVC composite film prepared in the comparative example were respectively subjected to performance tests, the test procedures were carried out according to the corresponding national standard requirements, and the measured conductivity and electromagnetic shielding performance were as shown in Table 1.
Table 1 composite film property comparison table
| conductivity/(S/cm) | Electromagnetic shielding performance (EMISE) | |
| Example 1 | 17.3 | 38.2dB |
| Example 2 | 12.1 | 32.8dB |
| Example 3 | 11.5 | 30.5dB |
| Comparative example | 3.1 | 19.5dB |
As can be seen from table 1, the electromagnetic shielding performance of the carbon nanotube and the ferroferric oxide is significantly improved after the hydrotalcite-like compound is modified, and the electromagnetic shielding performance gradually increases as the volume ratio of the hydrotalcite-like compound to the carbon nanotube and the ferroferric oxide decreases.
The embodiments of the present invention have been described in detail, but the present invention is not limited to the described embodiments. Various changes, modifications, substitutions and alterations to these embodiments will occur to those skilled in the art without departing from the spirit and scope of the present invention.
Claims (8)
1. A preparation method of a flexible electromagnetic shielding PVC composite film is characterized by comprising the following steps:
s10: ultrasonically dispersing the polymer/hydrotalcite-like single-layer nano material into water, and uniformly dispersing to obtain a polymer/hydrotalcite-like single-layer nano turbid liquid;
s20: ultrasonically dispersing a hydroxyl carbon nano tube into water, and uniformly dispersing to obtain a hydroxyl carbon nano tube solution; mixing the polymer/hydrotalcite-like single-layer nanometer suspension with the hydroxyl carbon nanotube solution, generating a precipitate immediately under the action of electrostatic self-assembly, and centrifuging, washing with water, washing with methanol and drying the precipitate to obtain a modified carbon nanotube composite material;
s30: adding the polymer/hydrotalcite-like single-layer nano turbid liquid into a solution for preparing ferroferric oxide by adopting a coprecipitation method, and slowly dropwise adding 40mL of NH 3 ·H 2 O is atCrystallizing at 80 ℃ for 1h, centrifuging the slurry obtained by crystallization to obtain a precipitate, and respectively centrifuging and washing the precipitate for 5-10 times by using ethanol and water to obtain a modified ferroferric oxide nano composite material;
s40: putting 15-20% of PVC, 6-10% of modified carbon nanotube composite material, 6-10% of modified ferroferric oxide nanocomposite material, 2-6% of pore-forming agent and 54-71% of solvent into a 250ml three-neck flask according to the mass percentage, heating, stirring, dissolving and mixing at 70 ℃, and fully defoaming to obtain a polymer solution; and scraping the polymer solution on the surface of the non-woven fabric at the speed of 0.1-5.0m/s into a flat membrane at room temperature, cooling by air, solidifying and forming in water at room temperature, soaking for 12-24h to remove the solvent and the pore-forming agent, taking out and drying to obtain the flexible electromagnetic shielding PVC composite membrane with the membrane thickness of 0.8-1.5mm.
2. The method for preparing a flexible electromagnetic shielding PVC composite film according to claim 1, wherein in the step S10, the preparation process of the polymer/hydrotalcite-like single-layer nano material comprises the following steps:
s11: dispersing a polymer A containing carboxyl or carboxylic anhydride groups into an aqueous solution, and adding an excessive alkali solution for treatment to obtain a polymer ion salt solution;
s12: dissolving divalent metal ion salt and trivalent metal ion salt in water to obtain mixed metal ion salt solution;
s13: under the protection of inert gas at a certain temperature, dropwise adding the mixed metal ion salt solution into the polymer salt solution, and adjusting the pH value in the reaction process by using an alkali solution to ensure that the pH value of a system is not more than 10;
s14: and (4) centrifuging the slurry obtained after the reaction in the step (S13) is finished, and centrifuging and washing the precipitate to be neutral by using ethanol and water respectively to obtain the polymer/hydrotalcite-like single-layer nano material.
3. The method for preparing a flexible electromagnetic shielding PVC composite film according to claim 2, wherein the divalent metal ion in the divalent metal ion salt is Mg 2+ Of trivalent metalsThe trivalent metal ion in the ionic salt is Al 3+ The anion in the mixed metal ion salt solution is NO 3- The molar ratio of the divalent metal ions to the trivalent metal ions is (2-5): 1; the mass ratio of the trivalent metal ion salt to the polymer A is 1 (1-10); the polymer A is one of polyacrylic acid, ethylene acrylic acid copolymer and polystyrene/carboxylic anhydride functional group copolymer; the reaction temperature in the step S13 is 60-80 ℃, the inert gas is nitrogen or argon, the reaction time is 6-24h, and the alkali solution is ammonia water, a sodium hydroxide solution or a potassium hydroxide solution.
4. The method for preparing a flexible electromagnetic shielding PVC composite film according to claim 1, wherein in the step S20, the concentration ratio of the polymer/hydrotalcite-like single-layer nano-material suspension to the hydroxyl carbon nanotube solution is (1.
5. The method for preparing a flexible electromagnetic shielding PVC composite film according to claim 1, wherein in step S30, the preparation process of the solution of ferroferric oxide by using a coprecipitation method comprises the following steps: 0.06mol of FeCl 3 ·6H 2 O and 0.03mol of FeSO 4 ·7H H 2 Adding O into a three-neck flask containing a certain volume of deionized water, and performing ultrasonic treatment for 5min to dissolve the O to obtain the product.
6. The method for preparing a flexible electromagnetic shielding PVC composite film according to claim 5, wherein in the step S30, the volume ratio of the polymer/hydrotalcite-like compound single-layer nano-suspension to the solution for preparing ferroferric oxide by a coprecipitation method is 1-1.
7. The method for preparing a flexible electromagnetic shielding PVC composite film according to claim 1, wherein in step S40, the pore-forming agent is polyethylene glycol with a molecular weight of one of 200g/mol, 400g/mol, 600g/mol, 800g/mol, and 1000 g/mol; the solvent is one of N, N-dimethylformamide, N-dimethylacetamide, N-methylpyrrolidone and dimethyl sulfoxide; the non-woven fabric is polyethylene terephthalate or polyamide non-woven fabric, and the thickness of the non-woven fabric is 50-150 mu m.
8. A flexible electromagnetic shielding PVC composite film, which is characterized by being prepared by the preparation method of any one of claims 1 to 7.
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Citations (16)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH10330727A (en) * | 1997-05-28 | 1998-12-15 | Jsr Corp | Surface treating agent for porous material |
| US20010028946A1 (en) * | 2000-03-30 | 2001-10-11 | Jae-Mok Ha | Wallpaper for shielding electromagnetic waves |
| JP2004162203A (en) * | 2002-11-13 | 2004-06-10 | Norio Tsubokawa | Modified carbon nanofiber, resin composition comprising the same and coating |
| US20100009165A1 (en) * | 2008-07-10 | 2010-01-14 | Zyvex Performance Materials, Llc | Multifunctional Nanomaterial-Containing Composites and Methods for the Production Thereof |
| CN102284264A (en) * | 2011-06-15 | 2011-12-21 | 北京化工大学 | Method for preparing hydrotalcite coated ferroferric oxide microspheres |
| CN103443870A (en) * | 2010-09-23 | 2013-12-11 | 应用纳米结构方案公司 | CNT-infused fiber as a self shielding wire for enhanced power transmission line |
| CN105968412A (en) * | 2016-06-03 | 2016-09-28 | 西南科技大学 | Ferrocene modified ternary hydrotalcite flame-retardant smoke inhibitor and preparation method and application thereof |
| CN107403941A (en) * | 2017-07-24 | 2017-11-28 | 湖北工程学院 | Compound alkaline polyelectrolyte film of hydrotalcite enveloped carbon nanometer tube and preparation method thereof |
| CN108314007A (en) * | 2017-01-18 | 2018-07-24 | 中国石油化工股份有限公司 | A kind of nickel-carbon nano tube compound material and preparation method thereof |
| CN110358136A (en) * | 2019-07-04 | 2019-10-22 | 武汉纺织大学 | A kind of composite foam film and preparation method thereof |
| CN111749028A (en) * | 2020-07-07 | 2020-10-09 | 苏州康丽达精密电子有限公司 | Multilayer composite graphene electromagnetic shielding material and preparation method thereof |
| CN114775267A (en) * | 2022-04-12 | 2022-07-22 | 南通大学 | Electromagnetic shielding non-woven fabric and preparation method thereof |
| CN114872353A (en) * | 2022-05-10 | 2022-08-09 | 浙江理工大学 | Preparation method and application of flame-retardant electromagnetic shielding film based on nylon waste silk |
| CN114956144A (en) * | 2022-06-07 | 2022-08-30 | 秦迎 | Hydrotalcite single-layer nano material and preparation method thereof |
| CN115124061A (en) * | 2022-06-07 | 2022-09-30 | 秦迎 | Polymer modified hydrotalcite-like nano composite material and preparation method thereof |
| CN115141439A (en) * | 2022-07-18 | 2022-10-04 | 湖北大学 | Foamed PVC composite material with electromagnetic shielding performance and preparation method and application thereof |
-
2022
- 2022-10-22 CN CN202211297748.3A patent/CN115652650A/en active Pending
Patent Citations (16)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH10330727A (en) * | 1997-05-28 | 1998-12-15 | Jsr Corp | Surface treating agent for porous material |
| US20010028946A1 (en) * | 2000-03-30 | 2001-10-11 | Jae-Mok Ha | Wallpaper for shielding electromagnetic waves |
| JP2004162203A (en) * | 2002-11-13 | 2004-06-10 | Norio Tsubokawa | Modified carbon nanofiber, resin composition comprising the same and coating |
| US20100009165A1 (en) * | 2008-07-10 | 2010-01-14 | Zyvex Performance Materials, Llc | Multifunctional Nanomaterial-Containing Composites and Methods for the Production Thereof |
| CN103443870A (en) * | 2010-09-23 | 2013-12-11 | 应用纳米结构方案公司 | CNT-infused fiber as a self shielding wire for enhanced power transmission line |
| CN102284264A (en) * | 2011-06-15 | 2011-12-21 | 北京化工大学 | Method for preparing hydrotalcite coated ferroferric oxide microspheres |
| CN105968412A (en) * | 2016-06-03 | 2016-09-28 | 西南科技大学 | Ferrocene modified ternary hydrotalcite flame-retardant smoke inhibitor and preparation method and application thereof |
| CN108314007A (en) * | 2017-01-18 | 2018-07-24 | 中国石油化工股份有限公司 | A kind of nickel-carbon nano tube compound material and preparation method thereof |
| CN107403941A (en) * | 2017-07-24 | 2017-11-28 | 湖北工程学院 | Compound alkaline polyelectrolyte film of hydrotalcite enveloped carbon nanometer tube and preparation method thereof |
| CN110358136A (en) * | 2019-07-04 | 2019-10-22 | 武汉纺织大学 | A kind of composite foam film and preparation method thereof |
| CN111749028A (en) * | 2020-07-07 | 2020-10-09 | 苏州康丽达精密电子有限公司 | Multilayer composite graphene electromagnetic shielding material and preparation method thereof |
| CN114775267A (en) * | 2022-04-12 | 2022-07-22 | 南通大学 | Electromagnetic shielding non-woven fabric and preparation method thereof |
| CN114872353A (en) * | 2022-05-10 | 2022-08-09 | 浙江理工大学 | Preparation method and application of flame-retardant electromagnetic shielding film based on nylon waste silk |
| CN114956144A (en) * | 2022-06-07 | 2022-08-30 | 秦迎 | Hydrotalcite single-layer nano material and preparation method thereof |
| CN115124061A (en) * | 2022-06-07 | 2022-09-30 | 秦迎 | Polymer modified hydrotalcite-like nano composite material and preparation method thereof |
| CN115141439A (en) * | 2022-07-18 | 2022-10-04 | 湖北大学 | Foamed PVC composite material with electromagnetic shielding performance and preparation method and application thereof |
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