CN110922709B - Conductive polymer composite wave-absorbing material and preparation method thereof - Google Patents
Conductive polymer composite wave-absorbing material and preparation method thereof Download PDFInfo
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Abstract
The invention provides a preparation method of a conductive polymer composite wave-absorbing material. The method comprises the following steps of preparing the nano material/conductive polymer composite wave absorbing agent. And secondly, preparing the nano material/conductive polymer/adhesive composite material. And step three, preparing the composite wave-absorbing coating. Fourthly, the composite wave-absorbing coating is hot-pressed and rolled. By the preparation method, the wave absorbing agent can be uniformly dispersed in the binder, so that the wave absorbing effect of each part of the composite material is more uniform. Meanwhile, the silicon nitride and the silicon carbide have unique three-dimensional space architecture and excellent wave-absorbing performance under a low frequency band, so that the toughness and the tensile strength of the composite wave-absorbing material can be increased, and the absorption frequency range of the composite material is widened.
Description
Technical Field
The invention belongs to the technical field of electromagnetic wave absorbing materials, and particularly relates to a conductive polymer composite wave absorbing material and a preparation method thereof.
Background
In recent years, the intelligent electronic information industry has made a leap-type progress, and the rising of 5G is the application of NFC and wireless charging technologies. Meanwhile, mobile phones, computers and tablets are also developing in the light and thin directions. This puts more severe requirements on various components inside the electronic products. At present, components in electronic products are mainly presented in an integrated circuit mode, and various electronic components cannot avoid generating electromagnetic interference on other components around the electronic components when working simultaneously, so that the normal functions of the electronic components are influenced. In order to avoid the problem, the wave-absorbing material is produced. The wave-absorbing materials can be classified into dielectric type, resistive type and magnetic loss type according to different absorption modes. At present, magnetic loss type alloy materials such as iron silicon, iron silicon aluminum and the like are widely applied to the electronic industry due to excellent wave absorbing performance. The wave-absorbing material mainly comprises alloy powder and a binder. The alloy powder in the material has a large proportion, so that the produced wave-absorbing material has the defects of frangibility, thickness and the like.
In addition, a composite electromagnetic shielding film for FPC is disclosed, in which a dielectric type silicon carbide, a resistive type conductive polymer, and a resin are simply blended to form an electromagnetic wave absorbing layer. The electromagnetic wave absorbing layer prepared by the simple physical mixing mode has nonuniform wave absorbing performance at all positions of the prepared composite material due to nonuniform mixing of the conductive polymer and the silicon carbide, different wave absorbing frequency bands of the two wave absorbing materials and the like.
Disclosure of Invention
In view of the above disadvantages of the prior art, the present invention aims to provide a conductive polymer composite wave-absorbing material, especially a slurry formulation and a preparation method of a wave-absorbing agent, which realizes the lightness, thinness, excellent mechanical strength, broadband and uniform wave-absorbing performance of each part of the wave-absorbing material.
In order to achieve the purpose, the invention provides a preparation method of a conductive polymer composite wave-absorbing material, which comprises the following steps.
Firstly, preparing a wave absorbing agent.
The wave absorber is prepared by the following components through ultrasonic treatment, stirring, centrifugation, suction filtration and drying: the dielectric wave-absorbing material comprises a dielectric wave-absorbing nano material, a dispersing agent or a coupling agent, an anti-settling agent, a conductive polymer and deionized water. The dielectric medium type wave-absorbing nano material is at least one of silicon carbide and silicon nitride; the coupling agent is a silane coupling agent; the dispersing agent is at least one of fatty acids, aliphatic amides, paraffin and low molecular wax; the anti-settling agent is at least one of a urea modified polyurethane solution and a modified urea solution; the conductive polymer is at least one of polyaniline, polypyrrole and polythiophene.
The method comprises the following steps: the mode of adding the dispersing agent is adopted. The addition of the dispersing agent can reduce the surface energy of the nano material, improve the dispersing performance of the nano material and facilitate the nano material to be dispersed in the conductive polymer in the stirring process.
Firstly, 2-20 parts of dielectric wave-absorbing nano material, 0.1-0.4 part of anti-settling agent and 0.8-2 parts of dispersing agent are subjected to ultrasonic treatment in 100-160 parts of deionized water for 5-10 min, and the nano material can be rapidly dispersed by the ultrasonic treatment. Then, mechanical stirring is carried out for 2-6 hours, and the rotating speed of the mechanical stirring is 2000-3000 r/min. And after uniform dispersion, adding 40-80 parts of conductive polymer into the mixture, and continuously stirring for 4-8 hours to obtain the nano material/conductive polymer. And centrifuging the obtained dispersion liquid by adopting a high-speed centrifuge, wherein the rotating speed of the centrifuge is 10000-30000 r/min, so as to obtain a precipitate. The precipitate was filtered off with suction. And finally, drying the precipitate in an oven at the temperature of 60-120 ℃.
The method 2 comprises the following steps: the mode of adding the coupling agent is adopted. The coupling agent contains two groups with different chemical properties, namely an organophilic group and an inotropic group, so that the coupling agent can be used as a molecular bridge to connect the nano material and the conductive polymer, thereby enhancing the interaction between the nano material and the conductive polymer.
Firstly, 2-20 parts of dielectric wave-absorbing nano material, 0.1-0.4 part of anti-settling agent and 40-80 parts of conductive polymer are mechanically stirred in 100-160 parts of deionized water for 2-6 hours, wherein the mechanical stirring speed is 2000-3000 r/min. And after uniform dispersion, adding 2-6 parts of coupling agent, and continuing to disperse for 4-8 hours to obtain the nano material/conductive polymer. Centrifuging the obtained dispersion liquid by using a high-speed centrifuge, wherein the rotating speed of the centrifuge is 10000-30000 r/min, so as to obtain a precipitate; the precipitate was filtered off with suction. And finally, drying the precipitate in an oven at the temperature of 60-120 ℃.
And secondly, preparing slurry for coating.
The conductive polymer composite wave-absorbing slurry comprises the following components in parts by mass: 1-3 parts of a wave absorbing agent, 1-3 parts of a rubber type resin and 20-40 parts of a solvent; the rubber type resin adhesive is styrene-ethylene-butylene-styrene block copolymer (SEBS); the solvent is at least one of toluene, xylene and ethyl acetate.
Firstly, dissolving rubber type resin in a solvent to obtain a rubber type resin solution, wherein the solid content of the rubber type resin is 5-15%; and mixing the wave absorbing agent and the rubber type resin solution, and transferring the mixture into a ball mill for ball milling for 2-4 h.
And step three, coating, drying and rolling.
And uniformly coating the ball-milled slurry on a base material through a coating process, and then drying and curing. Wherein the coating speed is 8-25 m/min, the thickness of the coated wet film is 150-250 μm, the drying and curing temperature is 50-120 ℃, and the thickness of the dried film after drying and curing is 30-50 μm; and carrying out hot pressing on the obtained dry film, wherein hot pressing equipment is a single-roller calender. The pressure is 100-150 kg, the hot pressing temperature is 160-200 ℃, and the hot pressing speed is 1-4 m/min.
Compared with the prior art, the invention has the following advantages.
1. Silicon carbide and silicon nitride are excellent dielectric wave absorbers, and Si/C/N is 100-106Hz has large dielectric loss and is a good wave-absorbing material under low frequency. The conductive polymer belongs to a resistance type wave absorbing agent, and is mainly characterized by having higher dielectric loss tangent, absorbing electromagnetic waves by means of electronic polarization or interface polarization attenuation of a medium, and having good wave absorbing effect at high frequency. By adding the dispersing agent, the surface energy of the silicon carbide and the silicon nitride is reduced, so that the silicon carbide and the silicon nitride are fully dispersed in the molecular gaps of the conducting polymer or the coupling agent is added, the nanometer material and the conducting polymer form a cross-linked network structure, and the dispersing of the nanometer material and the conducting polymer is more uniform. The wave-absorbing material prepared by the composite wave-absorbing agent has more uniform wave-absorbing performance at all parts and relatively stable wave-absorbing frequency band.
2. The nano silicon carbide and the silicon nitride have unique spatial structures, the nano silicon carbide and the silicon nitride are dispersed in macromolecules of the conductive polymer, so that the toughness of the conductive polymer can be improved, and interpenetrating networks can be formed among molecules after the conductive polymer and the binder are sufficiently ball-milled, so that the formed composite wave-absorbing material has higher tensile strength.
3. By adjusting the ratio of the types of the nano materials to the conductive polymer, the wave-absorbing material with different absorbing frequency bands and wave-absorbing effects can be obtained, and the adjustability of the absorbing frequency bands is strong.
Detailed Description
The technical solutions of the present invention will be described clearly and completely with reference to specific embodiments, 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.
Example 1.
1.5 parts of nano silicon carbide, 0.2 part of urea modified polyurethane and 2 parts of polyacrylamide are added into 120 parts of deionized water for ultrasonic treatment for 5min, and then mechanical stirring is carried out for 3h, wherein the mechanical stirring speed is 2500 r/min. And after uniform dispersion, adding 60 parts of polythiophene, continuously stirring for 4 hours to obtain silicon carbide/polythiophene dispersion liquid, centrifuging the obtained dispersion liquid by using a high-speed centrifuge, wherein the rotating speed of the centrifuge is 20000r/min to obtain a precipitate, filtering the obtained precipitate, drying the filtered precipitate in an oven at the temperature of 80 ℃ to obtain the silicon carbide/polythiophene wave absorbing agent.
2. 1 part of silicon carbide/polythiophene wave absorbing agent, 3 parts of SEBS resin and 20 parts of ethyl acetate are dissolved and mixed uniformly, the solution is transferred into a ball mill for ball milling, and the ball milling time is 4 hours to obtain slurry.
3. And uniformly coating the ball-milled slurry on a base material through a coating process, and then drying and curing. Wherein the coating speed is 12m/min, the thickness of the coated wet film is 250 μm, the drying and curing temperature is 110 ℃, and the thickness of the dried and cured film is 35 μm; and carrying out hot pressing on the obtained dry film, wherein hot pressing equipment is a single-roller calender, the pressure is 100 kg, the hot pressing temperature is 160 ℃, and the hot pressing speed is 2 m/min. The thickness of the film layer after hot pressing was 30 μm.
The prepared wave-absorbing material has high magnetic conductivity under 100 KHz-2 GHz. The tensile strength was 35 MPa. And cutting the wave-absorbing material subjected to hot pressing into a circular ring to test the magnetic conductivity, and carrying out parallel measurement for 5 times in the same batch. The test results were as follows: initial permeability at 1MHz was 181, 183, 180, 181, 184, respectively. The initial permeability at 1GHz was 227, 231, 239, 233, 235, respectively.
Example 2.
1. Adding 8 parts of nano silicon carbide, 0.2 part of urea modified polyurethane, 0.1 part of modified urea solution and 2 parts of polyacrylamide into 140 parts of deionized water, carrying out ultrasonic treatment for 5min, and then mechanically stirring for 4h at the rotating speed of 2500 r/min. After the dispersion is uniform, 60 parts of polythiophene is added and stirring is continued for 4 hours to obtain silicon carbide/polythiophene, the obtained emulsion is centrifuged by a high-speed centrifuge, the rotating speed of the centrifuge is 20000r/min to obtain precipitate, the obtained precipitate is filtered, and the filtered precipitate is dried in an oven at the temperature of 80 ℃.
2. 1 part of silicon carbide/polythiophene wave absorbing agent, 3 parts of SEBS resin and 20 parts of ethyl acetate are dissolved and mixed uniformly, and the solution is transferred into a ball mill for ball milling for 4 hours to obtain slurry. And transferring the solution into a ball mill for ball milling for 5 hours to obtain slurry.
3. Uniformly coating the ball-milled slurry on a release film through a coating process, and then drying and curing; wherein the coating speed is 10m/min, the thickness of the coated wet film is 250 μm, the drying and curing temperature is 110 ℃, and the thickness of the dried and cured film is 35 μm; and carrying out hot pressing on the obtained dry film, wherein hot pressing equipment is a single-roller calender, the pressure is 100 kg, the hot pressing temperature is 180 ℃, and the hot pressing speed is 2 m/min. The thickness of the film layer after hot pressing was 30 μm.
The prepared wave-absorbing material has high magnetic conductivity under 100 KHz-2 GHz. The tensile strength was 31 MPa. And cutting the wave-absorbing material subjected to hot pressing into a circular ring to test the magnetic conductivity, and carrying out parallel measurement for 5 times in the same batch. The test results were as follows: the initial permeability at 1MHz was 201, 199, 197, 203, 204, respectively. Initial permeability at 1GHz was 233, 237, 239, 235, 234, respectively.
Example 3.
1.5 parts of nano silicon carbide, 0.2 part of modified urea solution and 60 parts of polythiophene are added into deionized water and mechanically stirred for 3 hours, and the mechanical stirring speed is 2500 r/min. After the uniform dispersion, adding 4 parts of silane coupling agent, continuously stirring for 4 hours to obtain silicon carbide/polythiophene, centrifuging the obtained solution by adopting a high-speed centrifuge, obtaining a precipitate at the centrifuge rotating speed of 20000r/min, filtering the obtained precipitate, and drying the filtered precipitate in an oven at the temperature of 80 ℃.
2. Dissolving and uniformly mixing 2 parts of silicon carbide/polythiophene wave absorbing agent, 3 parts of SEBS resin and 20 parts of ethyl acetate, and transferring the solution into a ball mill for ball milling for 4 hours to obtain slurry.
3. Uniformly coating the ball-milled slurry on a release film through a coating process, and then drying and curing; wherein the coating speed is 12m/min, the thickness of the coated wet film is 250 μm, the drying and curing temperature is 110 ℃, and the thickness of the dried and cured film is 40 μm; and carrying out hot pressing on the obtained dry film, wherein hot pressing equipment is a single-roller calender, the pressure is 110 kg, the hot pressing temperature is 180 ℃, and the hot pressing speed is 2 m/min. The thickness of the film layer after hot pressing was 36 μm.
The prepared wave-absorbing material has high magnetic conductivity under 100 KHz-2 GHz. The tensile strength was 29 MPa. And cutting the wave-absorbing material subjected to hot pressing into a circular ring to test the magnetic conductivity, and carrying out parallel measurement for 5 times in the same batch. The test results were as follows: the initial permeability at 1MHz was 223, 220, 225, 223, 220, respectively. The initial permeability at 1GHz was 234, 231, 234, 236, 233 respectively.
Example 4.
1. Adding 2 parts of nano silicon carbide, 3 parts of silicon nitride, 0.2 part of urea modified polyurethane and 1 part of paraffin into deionized water, performing ultrasonic treatment for 10min, and then performing mechanical stirring for 4h at the mechanical stirring speed of 2500 r/min. After the uniform dispersion, 30 parts of polypyrrole and 30 parts of polyaniline are added and continuously stirred for 4 hours to obtain silicon nitride, silicon carbide/polypyrrole and polyaniline emulsions, a high-speed centrifuge is adopted to centrifuge the obtained emulsions, the rotation speed of the centrifuge is 25000r/min to obtain precipitates, the obtained precipitates are filtered, and the filtered precipitates are dried in an oven at the temperature of 80 ℃.
2. 1.5 parts of silicon carbide/polythiophene wave absorbing agent, 3 parts of SEBS resin and 20 parts of ethyl acetate are dissolved and mixed uniformly, the solution is transferred into a ball mill for ball milling, and the ball milling time is 4 hours to obtain slurry.
3. Uniformly coating the ball-milled slurry on a release film through a coating process, and then drying and curing; wherein the coating speed is 12m/min, the thickness of the coated wet film is 200 μm, the drying and curing temperature is 110 ℃, and the thickness of the dried and cured film is 30 μm; and carrying out hot pressing on the obtained dry film, wherein hot pressing equipment is a single-roller calender, the pressure is 115 kg, the hot pressing temperature is 160 ℃, and the hot pressing speed is 2 m/min. The thickness of the film layer after hot pressing was 27 μm.
The prepared wave-absorbing material has high magnetic conductivity under 10 KHz-2 GHz. The tensile strength was 30 MPa. And cutting the wave-absorbing material subjected to hot pressing into a circular ring to test the magnetic conductivity, and carrying out parallel measurement for 5 times in the same batch. The test results were as follows: the initial permeability at 1MHz was 160, 163, 165, 164, 160, respectively. Initial permeability at 1GHz was 177, 180, 181, 179, 180 respectively.
Comparative example 1.
1.5 parts of nano silicon carbide and 60 parts of polythiophene are simply mixed in a physical mode.
2. And (2) dissolving and uniformly mixing 1 part of the mixture obtained in the step (1), 3 parts of SEBS resin and 20 parts of ethyl acetate, and transferring the solution into a ball mill for ball milling for 4 hours to obtain slurry.
3. Uniformly coating the ball-milled slurry on a release film through a coating process, and then drying and curing; wherein the coating speed is 12m/min, the thickness of the coated wet film is 250 μm, the drying and curing temperature is 110 ℃, and the thickness of the dried film after drying and curing is 35 μm; and carrying out hot pressing on the obtained dry film, wherein hot pressing equipment is a single-roller calender, the pressure is 100 kg, the hot pressing temperature is 160 ℃, and the hot pressing speed is 2 m/min. The thickness of the film layer after hot pressing was 30 μm.
The prepared wave-absorbing material has unstable magnetic conductivity at 100 KHz-2 GHz. And the tensile strength fluctuation is large and is between 10 and 20 MPa. And cutting the wave-absorbing material subjected to hot pressing into a circular ring to test the magnetic conductivity, and carrying out parallel measurement for 5 times in the same batch. The test results were as follows: the initial permeability at 1MHz was 103, 167, 124, 133, 177, respectively. The initial permeability at 1GHz was 207, 134, 183, 139, 161, respectively.
Comparative example 2.
1.5 parts of nano silicon carbide and 60 parts of polythiophene are physically mixed.
2. And (2) dissolving and uniformly mixing 2 parts of the mixture obtained in the step (1), 3 parts of SEBS resin and 20 parts of ethyl acetate, and transferring the solution into a ball mill for ball milling for 4 hours to obtain slurry.
3. Uniformly coating the ball-milled slurry on a release film through a coating process, and then drying and curing; wherein the unreeling speed is 12m/min, the thickness of the coated wet film is 300 mu m, the drying and curing temperature is 110 ℃, and the thickness of the dried film after drying and curing is 120 mu m; and carrying out hot pressing on the obtained dry film, wherein hot pressing equipment is a single-roller calender, the hot pressing temperature is 160 ℃, and the hot pressing speed is 2 m/min. The thickness of the film layer after hot pressing was 100 μm.
The prepared wave-absorbing material has unstable magnetic conductivity at 100 KHz-2 GHz. And the tensile strength fluctuation is large and is between 9 and 17 MPa. And cutting the wave-absorbing material subjected to hot pressing into a circular ring to test the magnetic conductivity, and carrying out parallel measurement for 5 times in the same batch. The test results were as follows: initial permeability at 1MHz was 153, 177, 132, 159, 133, respectively. The initial permeability at 1GHz was 207, 134, 183, 139, 161, respectively.
Comparative examples 1 and 2 or 1 and 3 have found that increasing the proportion of nanomaterial in the conductive polymer, or increasing the proportion of nanomaterial/conductive polymer in the binder, can increase the absorption of electromagnetic waves. Comparing example 1 with comparative example 1, or example 2 with comparative example 2, it can be seen that the wave-absorbing material prepared by compounding the conductive polymer and the nano material has more uniform wave-absorbing performance and small fluctuation amplitude. In addition, as can be seen from comparing examples 1 and 3, the absorption of electromagnetic waves of different frequency bands can be realized by changing the types and the proportions of the nano materials. The above embodiments also fully illustrate that the composite wave-absorbing material prepared by the invention has strong adjustability and can be designed in a targeted manner according to different application scenes.
It will be apparent to those skilled in the art that various changes and modifications may be made in the invention without departing from the spirit and scope of the invention. Thus, if such modifications and variations of the present invention fall within the scope of the claims of the present invention and their equivalents, the present invention is also intended to include such modifications and variations.
Claims (5)
1. The conductive polymer composite wave-absorbing material is characterized by being prepared from the following components in parts by mass through mixing, coating and hot pressing: 1-3 parts of a wave absorbing agent, 1-3 parts of a rubber type resin and 20-40 parts of a solvent;
the wave absorber is prepared by the following components in parts by mass through ultrasonic treatment, stirring, centrifugation, suction filtration and drying: 2-20 parts of dielectric wave-absorbing nano material, 0.8-2 parts of dispersing agent or 2-6 parts of coupling agent, 0.1-0.4 part of anti-settling agent, 40-80 parts of conductive polymer and 100-160 parts of deionized water;
the dielectric wave-absorbing nano material in the wave absorbing agent is at least one of nano silicon carbide and nano silicon nitride;
the coupling agent is a silane coupling agent;
the dispersant is at least one of fatty acids, fatty acid amides, paraffin and low molecular wax;
the anti-settling agent is at least one of a urea modified polyurethane solution and a modified urea solution;
the conductive polymer is at least one of polyaniline, polypyrrole and polythiophene;
the rubber type resin is a styrene-ethylene-butylene-styrene block copolymer.
2. The conductive polymer composite wave-absorbing material of claim 1, wherein the solvent is at least one of toluene, xylene and ethyl acetate.
3. A preparation method of the conductive polymer composite wave-absorbing material as claimed in any one of claims 1 to 2, wherein when a dispersant is adopted, the wave-absorbing agent comprises the following preparation steps:
(1) adding the dielectric wave-absorbing nano material into deionized water containing an anti-settling agent and a dispersing agent, and carrying out ultrasonic treatment for 5-10 min;
(2) then, mechanical stirring is carried out for 2-6 hours, and the rotating speed of the mechanical stirring is 2000-3000 r/min; after uniform dispersion, adding the conductive polymer into the solution, and continuously stirring for 4-8 hours to obtain a nano material/conductive polymer dispersion solution;
(3) centrifuging the obtained dispersion liquid by adopting a high-speed centrifuge, wherein the rotating speed of the centrifuge is 10000-30000 r/min, and obtaining a precipitate;
(4) carrying out suction filtration on the precipitate obtained in the step (3);
(5) and drying the filtered precipitate in an oven at the temperature of 60-120 ℃.
4. A preparation method of the conductive polymer composite wave-absorbing material as claimed in any one of claims 1 to 2, wherein when a coupling agent is adopted, the wave-absorbing agent comprises the following preparation steps:
(1) adding the dielectric wave-absorbing nano material, the conductive polymer and the anti-settling agent into deionized water, and mechanically stirring for 2-6 hours at the mechanical stirring speed of 2000-3000 r/min;
(2) after uniform dispersion, adding a coupling agent, and continuing to disperse for 4-8 hours to obtain a nano material/conductive polymer dispersion liquid;
(3) centrifuging the obtained dispersion liquid by using a high-speed centrifuge, wherein the rotating speed of the centrifuge is 10000-30000 r/min, so as to obtain a precipitate;
(4) carrying out suction filtration on the obtained precipitate;
(5) and drying the precipitate in an oven at the temperature of 60-120 ℃.
5. A preparation method of the conductive polymer composite wave-absorbing material as claimed in any one of claims 1 to 2, characterized in that the preparation method comprises the following steps:
(1) dissolving rubber type resin in a solvent to obtain a resin solution, wherein the solid content of the rubber type resin is 5-15%;
(2) transferring the wave absorbing agent and the rubber type resin solution into a ball mill for ball milling for 2-4 h to obtain ball milling slurry;
(3) uniformly coating the ball-milling slurry on a base material through a coating process, and then drying and curing; wherein the coating speed is 8-25 m/min, the thickness of the coated wet film is 150-250 μm, the drying and curing temperature is 50-120 ℃, and the thickness of the dried and cured film is 30-50 μm;
(4) carrying out hot pressing on the obtained dry film, wherein hot pressing equipment is a single-roller calender; the pressure is 100-150 kg, the hot pressing temperature is 160-200 ℃, and the hot pressing speed is 1-4 m/min.
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| CN112029221A (en) * | 2020-09-04 | 2020-12-04 | 北京化工大学常州先进材料研究院 | Ionic gel/conductive polymer electromagnetic shielding material, preparation method and application thereof |
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