CN111849174A - Conductive rubber composition, conductive rubber and preparation method thereof - Google Patents
Conductive rubber composition, conductive rubber and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a conductive rubber composition, conductive rubber and a preparation method thereof, wherein the conductive rubber composition comprises the following components in parts by weight: 100 parts of rubber matrix, 5-30 parts of carbon nano tube, 1-20 parts of graphene, 0-100 parts of nano M-type barium ferrite, 2-10 parts of silane coupling agent and 1-10 parts of vulcanizing agent. The conductive rubber prepared from the conductive rubber composition can shield high-frequency electromagnetic waves in the frequency range of 1 GHz-110 GHz, the shielding effect is improved along with the increase of the frequency of the electromagnetic waves, and meanwhile, the conductive rubber also has high conductivity and high mechanical elasticity.
Description
Technical Field
The invention relates to the technical field of functional materials, in particular to a conductive rubber composition, conductive rubber and a preparation method thereof.
Background
Electromagnetic interference (EMI) shielding of electronic equipment and/or radiation sources is an important consideration in the reliable operation of equipment. The conductive rubber plays a significant role in the field of electromagnetic shielding due to the characteristics of good sealing property, low density, corrosion resistance, easy processing and forming and the like. The conventional conductive rubber is obtained by adding a conductive filler such as a carbon-based material, a metal material or a metal-plated material to a rubber base.
However, the conventional conductive rubber generally has a certain shielding effect only on low-frequency electromagnetic waves below 1GHz, and as the frequency of the electromagnetic waves increases, the shielding effect of the conventional conductive rubber on the electromagnetic waves decreases. With the release of 5G network frequency bands including Sub6GHz (low frequency) and mmWave (high frequency) and the continuous commercial sale of products such as 60GHz wi-Fi and 77GHz millimeter wave radars, the problem of EMI shielding in the fields of 5G communication and other high-frequency electromagnetic waves, smart car and other internet of things, broadband radars and the like cannot be solved by the traditional conductive rubber.
The prior art therefore remains to be improved.
Disclosure of Invention
In view of the defects of the prior art, the invention provides a conductive rubber composition, a conductive rubber and a preparation method thereof, aiming at overcoming the problem that the prior conductive rubber cannot effectively shield high-frequency electromagnetic waves.
The technical scheme provided by the invention is as follows:
the conductive rubber composition comprises the following components in parts by weight: 100 parts of rubber matrix, 5-30 parts of carbon nano tube, 1-20 parts of graphene, 0-100 parts of barium ferrite, 2-10 parts of silane coupling agent and 1-10 parts of vulcanizing agent.
The conductive rubber composition is characterized in that the rubber matrix is at least one of methyl vinyl silicone rubber, dimethyl silicone rubber, methyl phenyl vinyl silicone rubber and fluorine silicone rubber.
When the rubber matrix is a solid phase rubber matrix, the vulcanizing agent includes at least one of di-tert-butyl peroxide, dicumyl peroxide, 2, 5-dimethyl-2, 5-bis (tert-butylperoxy) hexane and a Pt catalyst.
The conductive rubber composition is characterized in that when the rubber matrix is a liquid phase rubber matrix, the vulcanizing agent comprises at least one of methyl triacetoxysilane, methyl triethoxysilane, methyl tributyrinoxime silane, hexafunctional ethylene siloxane, aniline methyl triethoxysilane and a Pt catalyst.
The vulcanizing agent is used for vulcanizing a rubber matrix under a certain condition, so that the linear molecular structure of the rubber is changed into a three-dimensional net structure through the bridging action of the vulcanizing agent, and the mechanical and physical properties of the rubber are obviously improved. The vulcanizing agent is further 1-6 parts by weight, and further 1-3 parts by weight.
The conductive rubber composition is characterized in that the carbon nanotubes are at least one of single-walled carbon nanotubes, double-walled carbon nanotubes and multi-walled carbon nanotubes. The carbon nano tube is used as a conductive filler, is dispersed in the rubber matrix and is used for improving the conductivity of the conductive rubber. The weight portion of the carbon nano tube is further 10-30 portions, and is further 20-30 portions.
The graphene is used as a dispersing agent and a softening agent, and is used for improving the dispersion condition of the carbon nano tube in the rubber matrix, improving the compatibility and affinity between the carbon nano tube and the rubber matrix, and improving the process performances of the conductive rubber, such as elongation, rebound resilience and the like. The graphene is further 1-10 parts by weight, and further 1-5 parts by weight.
The barium ferrite is a nano composite magnetic material, the barium ferrite can be nano M-type barium ferrite, and the barium ferrite is uniformly dispersed in the conductive rubber, so that the shielding effect of the conductive rubber on high-frequency electromagnetic waves can be further improved.
The silane coupling agent is at least one of vinyl triethoxysilane (A151), vinyl trimethoxysilane (A171), vinyl tris (beta-methoxyethoxy) silane (A172), gamma-mercaptopropyl trimethoxysilane (A189), gamma-aminopropyltriethoxysilane (KH-550) and n-octyltriethoxysilane (A137).
The silane coupling agent is used for increasing the affinity between fillers such as carbon nano tubes and a rubber matrix so as to enable the fillers to be tightly combined, and further improving various properties of the conductive rubber, and the common molecular formula of the silane coupling agent is RSiX, wherein R is an organic functional group which cannot be hydrolyzed, such as an epoxy group, a vinyl group, a methacrylate group and the like, and X is a hydrolyzable group, such as halogen, an alkoxy group, an acyloxy group and the like. The silane coupling agent is further 2-6 parts by weight, and further 2-3 parts by weight.
The conductive rubber is prepared from the conductive rubber composition.
The conductive rubber is used for shielding electromagnetic waves in a frequency range of more than 1GHz, further used for shielding electromagnetic waves in a frequency range of more than 3GHz, and further used for shielding electromagnetic waves in a frequency range of more than 10 GHz.
A method for preparing a conductive rubber, wherein the method comprises:
placing the rubber matrix, the carbon nano tube, the silane coupling agent, the graphene and the vulcanizing agent in parts by weight into a mixing roll for mixing to obtain a rubber compound, wherein the rubber matrix is a solid phase rubber matrix;
and molding and vulcanizing the rubber compound to obtain the conductive rubber.
The preparation method of the conductive rubber comprises the following steps of forming and vulcanizing the rubber compound to obtain the conductive rubber:
and (2) carrying out compression molding on the mixed rubber by adopting a flat vulcanizing machine, and then carrying out secondary vulcanization to obtain the conductive rubber, wherein the compression molding conditions are as follows: the mold pressing temperature is 150-200 ℃, and the mold pressing pressure is 100-200 MPa.
The preparation method of the conductive rubber comprises the following steps of forming and vulcanizing the rubber compound to obtain the conductive rubber:
and (2) carrying out extrusion molding on the rubber compound by using an extruder, and then carrying out secondary vulcanization to obtain the conductive rubber, wherein the conditions of the extrusion molding are as follows: the extrusion temperature is 200-300 ℃, and the extrusion pressure is 500-1500 PSI.
A method for preparing a conductive rubber, wherein the method comprises:
adding the rubber matrix, the carbon nano tube, the silane coupling agent and the graphene in parts by weight into a stirrer for dispersing and stirring to obtain a semi-finished intermediate adhesive, wherein the rubber matrix is a liquid-phase rubber matrix;
and adding a vulcanizing agent into the dispersion rubber under the conditions of room temperature and vacuum, stirring, and extruding the semi-finished intermediate rubber added with the vulcanizing agent to obtain the conductive rubber.
Has the advantages that: the invention discloses a conductive rubber composition, conductive rubber and a preparation method thereof, wherein the conductive rubber composition comprises the following components in parts by weight: 100 parts of rubber matrix, 5-30 parts of carbon nano tube, 1-20 parts of graphene, 0-100 parts of nano M-type barium ferrite, 2-10 parts of silane coupling agent and 1-10 parts of vulcanizing agent. The conductive rubber prepared from the conductive rubber composition can shield high-frequency electromagnetic waves in the frequency range of 1 GHz-110 GHz, the shielding effect is improved along with the increase of the frequency of the electromagnetic waves, and meanwhile, the conductive rubber also has high conductivity and high mechanical elasticity.
Detailed Description
The present invention provides a conductive rubber composition, and the purpose, technical scheme and effect of the present invention are more clear and definite, and the present invention is further described in detail below. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
Example 1
1. Conductive rubber composition
The conductive rubber composition of the embodiment comprises the following components in parts by weight: 100 parts of methyl vinyl silicone rubber, 20 parts of carbon nano tubes, 5 parts of graphene, 5 parts of gamma-mercaptopropyl trimethoxy silane and 4 parts of 2, 5-dimethyl-2, 5-bis (tert-butyl peroxy) hexane.
2. Conductive rubber
The conductive rubber of the present example was prepared from the above conductive rubber composition.
Specifically, the preparation method of the conductive rubber of the embodiment includes the following steps:
1) mixing the raw materials
Accurately weighing the components in parts by weight, and then placing the components in a three-roll mixing mill for mixing; and during mixing, controlling the mixing temperature to be 30 ℃ and the mixing time to be 60min to fully and uniformly disperse the components, and standing for 8h after sheet discharging to obtain the rubber compound.
2) Compression molding
And (3) carrying out high-temperature and high-pressure compression molding on the rubber compound by using a flat vulcanizing machine, wherein the compression molding temperature is 150-200 ℃, and the compression molding pressure is 100-200 MPa.
According to GB/T30142-2013< < method for measuring shielding effectiveness of planar electromagnetic shielding material > > the shielding effectiveness of the conductive rubber material is measured, wherein the measuring instrument adopts a spectrum analyzer with the model number of E4447A and a signal generator with the model number of E8257D. The measurement results were as follows:
as can be seen from the above table, for electromagnetic waves in the frequency range of 1 to 40GHz, the conductive rubber of the present embodiment can achieve 40 to 80dB electromagnetic shielding effectiveness, and further, for electromagnetic waves in the frequency range of 10 to 40GHz, the conductive rubber of the present embodiment can achieve 55 to 80dB electromagnetic shielding effectiveness, and further, for electromagnetic waves in the frequency range of 25 to 40GHz, the conductive rubber of the present embodiment can achieve 60 to 80dB electromagnetic shielding effectiveness.
In addition, when the frequency of the electromagnetic wave is above 1GHz, the shielding effect of the conductive rubber of the embodiment increases with the increase of the frequency of the electromagnetic wave, while the shielding effect of the traditional conductive rubber such as Ni/C, Ag/Al, Ag/Cu and the like decreases with the increase of the frequency of the electromagnetic wave when the traditional conductive rubber shields the high-frequency electromagnetic wave, and the shielding effect decreases more obviously after 10 GHz.
In practical application, when the conductive rubber is applied to 100G and 400G optical modules or sub6 and higher frequency chip terminals, compared with the traditional conductive rubber, the shielding effect of reducing noise by 2-10 dB can be achieved.
Example 2
1. Conductive rubber composition
The conductive rubber composition of the embodiment comprises the following components in parts by weight: 100 parts of methyl vinyl silicone rubber, 25 parts of carbon nano tube, 5 parts of graphene, 7 parts of n-octyl triethoxysilane and 3 parts of Pt catalyst.
2. Conductive rubber
The conductive rubber of the present example was prepared from the above conductive rubber composition.
Specifically, the preparation method of the conductive rubber of the embodiment includes the following steps:
1) mixing the raw materials
Accurately weighing the components in parts by weight, and then placing the components in a three-roll mixing mill for mixing; and during mixing, controlling the mixing temperature to be 30 ℃ and the mixing time to be 60min to fully and uniformly disperse the components, and standing for 8h after sheet discharging to obtain the rubber compound.
2) Extrusion molding
Extruding and molding the rubber compound by using an extruder, and then performing secondary vulcanization; wherein the extrusion temperature is controlled to be 210 ℃, the extrusion pressure is 1000PSI, the temperature of the second-stage vulcanization is 210 ℃, and the time is 300min, so as to prepare the conductive rubber.
The volume resistivity of the conductive rubber and the maximum volume resistivity after thermal aging are detected to reach 0.5 omega cm by using a Mil-DTL-83528C method, and the tensile strength and the elongation at break of the conductive rubber are respectively detected to be 3.0Mpa and 300 percent by using an ASTM D412 method.
The embodiment can be effectively applied to high-frequency and high-speed electromagnetic wave shielding places, can achieve the shielding effect of reducing noise by 2-10 dB relative to the traditional conductive rubber, and has high conductivity and high mechanical elasticity.
Example 3
1. Conductive rubber composition
The conductive rubber composition of the embodiment comprises the following components in parts by weight: 100 parts of alpha, omega-dihydroxy dimethyl siloxane, 10 parts of carbon nano tube, 2 parts of graphene, 10 parts of gamma-aminopropyl triethoxysilane and 3 parts of hexafunctional ethylene siloxane.
2. Conductive rubber
The conductive rubber of the present example was prepared from the above conductive rubber composition.
Specifically, the preparation method of the conductive rubber of the embodiment includes the following steps:
1) dispersing and stirring
Accurately weighing the components according to the parts by weight, adding the other components except the hexa-functionality ethylene siloxane into a planetary stirrer, and dispersing and stirring to obtain the dispersion glue. Wherein the stirring temperature is 100 ℃, and the stirring time is 120 min.
2) Extrusion packaging
Cooling the dispersion glue to room temperature, adding hexa-functional ethylene siloxane into the dispersion glue in a vacuum state, stirring for 10min, extruding the carbon nano tube conductive rubber, discharging and tubing. The conductive rubber of the embodiment is packaged in vacuum and stored at low temperature.
The conductive rubber of the embodiment is liquid conductive rubber, has good fluidity and thixotropy, has the minimum dispensing width of 0.3mm, simultaneously keeps the height before room temperature vulcanization from collapsing, and has high elasticity and high shielding efficiency after vulcanization. In practical application, the conductive rubber of the embodiment can be applied to high-frequency electromagnetic wave leakage places with narrow gaps, and can achieve the shielding effect of reducing noise by 2-10 dB compared with the traditional conductive rubber.
Example 4
1. Conductive rubber composition
The conductive rubber composition of the embodiment comprises the following components in parts by weight: 100 parts of methyl vinyl silicone rubber, 10 parts of carbon nano tubes, 2 parts of graphene, 50 parts of M-type nano barium ferrite, 3 parts of gamma-mercaptopropyl trimethoxy silane and 4 parts of 2, 5-dimethyl-2, 5-bis (tert-butyl peroxy) hexane.
2. Conductive rubber
The conductive rubber of the present example was prepared from the above conductive rubber composition.
Specifically, the preparation method of the conductive rubber of the embodiment includes the following steps:
1) mixing the raw materials
Accurately weighing the components in parts by weight, and then placing the components in a three-roll mixing mill for mixing; and during mixing, controlling the mixing temperature to be 30 ℃ and the mixing time to be 60min to fully and uniformly disperse the components, and standing for 8h after sheet discharging to obtain the rubber compound.
2) Compression molding
And (3) carrying out high-temperature and high-pressure compression molding on the rubber compound by using a flat vulcanizing machine, wherein the compression molding temperature is 150-200 ℃, and the compression molding pressure is 100-200 MPa.
The network analyzer and the special waveguide jig are used for testing the attenuation suppression effect of the electromagnetic interference on the conductive rubber sample of the embodiment, and the result is as follows:
as can be seen from the above table, the conductive rubber of the present embodiment has an electromagnetic interference attenuation effect of 30 to 65dB for electromagnetic wave energy in a frequency range of 20 to 80GHz, further has an electromagnetic interference attenuation effect of 40 to 65dB for electromagnetic wave energy in a frequency range of 40 to 80GHz, and further has an electromagnetic interference attenuation effect of 60 to 65dB for electromagnetic wave energy in a frequency range of 60 to 80 GHz.
In addition, when the frequency of the electromagnetic wave is above 20GHz, the shielding effect of the conductive rubber of the embodiment increases with the increase of the frequency of the electromagnetic wave, and the shielding effect of the conventional conductive rubber such as Ni/C, Ag/Al, Ag/Cu, etc. is obviously decreased with the increase of the frequency of the electromagnetic wave when shielding the high-frequency electromagnetic wave above 10 GHz.
In practical application, the conductive rubber of the embodiment can realize good and effective electromagnetic interference suppression and isolation on hundreds of channels integrated array antennas in 60GHz wireless router products. The isolation wall made of the conductive rubber of the embodiment can effectively solve the interference of the high-frequency electromagnetic wave space radiation to the chip between the chip area of the 77GHz millimeter wave radar and the radar transmitting antenna array. Similarly, the frequency of a 5G mobile phone in a millimeter waveband is above 20GHz (north american authorized band 27.5-28.35 GHz, 37-40 GHz, european advanced band 24.25-27.5 GHz, etc.), the layout space of the array antenna is small, the number of channels is large, and it is more necessary to isolate and suppress electromagnetic waves.
Example 5
1. Conductive rubber composition
The conductive rubber composition of the embodiment comprises the following components in parts by weight: 100 parts of methyl vinyl silicone rubber, 18 parts of carbon nano tubes, 3 parts of graphene, 3 parts of gamma-aminopropyltriethoxysilane and 3 parts of 2, 5-dimethyl-2, 5-bis (tert-butylperoxy) hexane.
2. Conductive rubber
The conductive rubber of the present example was prepared from the above conductive rubber composition.
Specifically, the preparation method of the conductive rubber of the embodiment includes the following steps:
1) mixing the raw materials
Accurately weighing the components in parts by weight, and then placing the components in a three-roll mixing mill for mixing; and during mixing, controlling the mixing temperature to be 30 ℃ and the mixing time to be 60min to fully and uniformly disperse the components, and standing for 8h after sheet discharging to obtain the rubber compound.
2) Extrusion molding
Extruding and molding the rubber compound by using an extruder, and then performing secondary vulcanization; wherein the extrusion temperature is controlled to be 200-300 ℃, the extrusion pressure is controlled to be 500-1500 PSI, the temperature of the second-stage vulcanization is 210 ℃, and the time is 300min, so that the conductive rubber is prepared.
The embodiment can continuously extrude the conductive rubber with the diameter of more than 20mm and the large section size, the resistance of the rubber strip can reach less than 10 omega/cm, and the tensile strength and the elongation at break can simultaneously reach more than 3.0MPa and 300 percent.
In practical application, the conductive rubber of the embodiment can be applied to new energy or intelligent automobiles, and places such as aerospace and aviation which have high requirements on shielding effectiveness and light weight.
Example 6
1. Conductive rubber composition
The conductive rubber composition of the embodiment comprises the following components in parts by weight: 100 parts of alpha, omega-dihydroxy dimethyl siloxane, 15 parts of carbon nano tube, 5 parts of graphene, 30 parts of M-type nano barium ferrite, 10 parts of gamma-aminopropyl triethoxysilane and 6 parts of methyl tributyrinoxime silane.
2. Conductive rubber
The conductive rubber of the present example was prepared from the above conductive rubber composition.
Specifically, the preparation method of the conductive rubber of the embodiment includes the following steps:
1) dispersing and stirring
Accurately weighing the components according to the weight parts, adding the other components except the methyl tributyl ketoxime silane into a planetary stirrer, and carrying out dispersion stirring. Stirring temperature is 100 deg.C, and stirring time is 120 min.
2) Extrusion packaging
Cooling to room temperature, adding methyl tributyl ketoxime silane under vacuum state, stirring for 10min, extruding carbon nanotube conductive rubber, discharging and tubing. The conductive rubber of the embodiment is packaged in vacuum and stored at low temperature.
The conductive rubber of the embodiment is liquid conductive rubber, has good fluidity and thixotropy, and has high elasticity and high shielding efficiency after vulcanization. In practical application, the electromagnetic interference between antennas of a broadband (sweep frequency interval of 300 MHz-40 GHz) phased array radar is well shielded, so that the problem that the traditional shielding material, metal material or metal filler conductive rubber and the like cannot inhibit the electromagnetic interference is solved.
The conductive glue of the embodiment can achieve the shielding effect of reducing noise by 5-10 dB aiming at the chip electromagnetic interference resistance of a Sub6 frequency band (below 6 GHz) 5G mobile phone and a millimeter wave band 5G mobile phone.
Example 7
1. Conductive rubber composition
The conductive rubber composition of the embodiment comprises the following components in parts by weight: 100 parts of fluorosilicone rubber, 10 parts of carbon nano tubes, 5 parts of graphene, 5 parts of vinyl triethoxysilane, and 4 parts of 2, 5-dimethyl-2, 5-bis (tert-butylperoxy) hexane.
2. Conductive rubber
The conductive rubber of the present example was prepared from the above conductive rubber composition.
Specifically, the preparation method of the conductive rubber of the embodiment includes the following steps:
1) mixing the raw materials
Accurately weighing the components in parts by weight, and then placing the components in a mixing roll for mixing; and during mixing, controlling the mixing temperature to be 30 ℃ and the mixing time to be 60-90 min, fully and uniformly dispersing the components, and standing for 8h after sheet discharging to obtain the mixed rubber.
2) Compression molding
And (3) carrying out high-temperature and high-pressure compression molding on the rubber compound by adopting a flat vulcanizing machine. The mold pressing temperature is 150-200 ℃, and the mold pressing pressure is 100-200 MPa.
The conductive rubber of the embodiment can be applied to the use places needing high temperature resistance and oil immersion resistance, such as sealing of aircraft doors, aviation plug connectors and the like, electromagnetic shielding and the like.
Example 8
1. Conductive rubber composition
The conductive rubber composition of the embodiment comprises the following components in parts by weight: 100 parts of methyl vinyl silicone rubber, 15 parts of carbon nano tubes, 2 parts of graphene, 20 parts of M-type nano barium ferrite, 5 parts of vinyl triethoxysilane, and 3 parts of vulcanizing agent 2, 5-dimethyl-2, 5-bis (tert-butylperoxy) hexane.
2. Conductive rubber
The conductive rubber of the present example was prepared from the above conductive rubber composition.
Specifically, the preparation method of the conductive rubber of the embodiment includes the following steps:
1) mixing the raw materials
Accurately weighing the components in parts by weight, and then placing the components in a mixing roll for mixing; and during mixing, controlling the mixing temperature to be 30 ℃ and the mixing time to be 60min to fully and uniformly disperse the components, and standing for 8h after sheet discharging to obtain the rubber compound.
2) Compression molding
And (3) carrying out high-temperature and high-pressure compression molding on the rubber compound by adopting a flat vulcanizing machine. The mold pressing temperature is 150-200 ℃, and the mold pressing pressure is 100-200 MPa.
According to GB/T30142-2013< < method for measuring shielding effectiveness of planar electromagnetic shielding material > > the shielding effectiveness of the conductive rubber material is measured, wherein the measuring instrument adopts a spectrum analyzer, model E4447A, a signal generator, model E8257D. The measurement results were as follows:
from the above table, for electromagnetic waves in the frequency range of 0.5 to 40GHz, the conductive rubber of the present embodiment can achieve 35 to 60dB of electromagnetic shielding effectiveness, further, for electromagnetic waves in the frequency range of 1 to 40GHz, the conductive rubber of the present embodiment can achieve 40 to 60dB of electromagnetic shielding effectiveness, further, for electromagnetic waves in the frequency range of 10 to 40GHz, the conductive rubber of the present embodiment can achieve 55 to 60dB of electromagnetic shielding effectiveness, further, for electromagnetic waves in the frequency range of 20 to 40GHz, and the conductive rubber of the present embodiment can achieve 57 to 60dB of electromagnetic shielding effectiveness.
In addition, when the frequency of the electromagnetic wave is above 0.5GHz, the shielding effect of the conductive rubber of the embodiment is increased along with the increase of the frequency of the electromagnetic wave, and the shielding effect of the traditional conductive rubber is reduced along with the increase of the frequency of the electromagnetic wave when the traditional conductive rubber such as Ni/C, Ag/Al, Ag/Cu and the like shields the high-frequency electromagnetic wave.
The conductive rubber of the embodiment can realize the 5G communication base station supplied to Sub6 (below 6 GHz) and millimeter wave band (above 20 GHz), and is used for waterproof sealing and electromagnetic shielding.
Example 9
1. Conductive rubber composition
The conductive rubber composition of the embodiment comprises the following components in parts by weight: 100 parts of methyl vinyl silicone rubber, 25 parts of carbon nano tubes, 5 parts of graphene, 10 parts of M-type nano barium ferrite, 5 parts of gamma-aminopropyltriethoxysilane and 5 parts of 2, 5-dimethyl-2, 5-bis (tert-butylperoxy) hexane.
2. Conductive rubber
The conductive rubber of the present example was prepared from the above conductive rubber composition.
Specifically, the preparation method of the conductive rubber of the embodiment includes the following steps:
1) mixing the raw materials
Accurately weighing the components in parts by weight, and then placing the components in a three-roll mixing mill for mixing; and during mixing, controlling the mixing temperature to be 30 ℃ and the mixing time to be 60min to fully and uniformly disperse the components, and standing for 8h after sheet discharging to obtain the rubber compound.
2) Extrusion molding
Extruding and molding the rubber compound by using an extruder, and then performing secondary vulcanization; wherein the extrusion temperature is controlled to be 200-300 ℃, the extrusion pressure is controlled to be 500-1500 PSI, the temperature of the second-stage vulcanization is 210 ℃, and the time is 300min, so that the conductive rubber is prepared.
The embodiment can continuously extrude the conductive rubber with the diameter of 1 mm-10 mm, the resistance of the rubber strip can reach below 200-50 omega/cm, the tensile strength and the elongation at break can simultaneously reach above 1.0-3.0 MPa and 200%, and the compression permanent deformation can reach below 30% (the calculation method B is equivalent to about 8% of the calculation method A).
The conductive rubber of the embodiment can realize the 5G communication base station supplied to Sub6 (below 6 GHz) and millimeter wave band (above 20 GHz), and is used for waterproof sealing and electromagnetic shielding.
Example 10
1. Conductive rubber composition
The conductive rubber composition of the embodiment comprises the following components in parts by weight: 100 parts of alpha, omega-dihydroxy dimethyl siloxane, 10 parts of carbon nano tube, 10 parts of graphene, 6 parts of gamma-aminopropyl triethoxysilane and 6 parts of methyl triethoxysilane.
2. Conductive rubber
The conductive rubber of the present example was prepared from the above conductive rubber composition.
Specifically, the preparation method of the conductive rubber of the embodiment includes the following steps:
1) dispersing and stirring
Accurately weighing the components according to the parts by weight, adding the other components except the methyl triethoxysilane into a planetary mixer, and dispersing and stirring to obtain the dispersion glue. Stirring temperature is 100 deg.C, and stirring time is 120 min.
2) Extrusion packaging
Cooling the dispersion glue to room temperature, adding methyl triethoxysilane in a vacuum state, stirring for 10min, extruding the carbon nanotube conductive rubber, discharging and tubing. The conductive rubber of the embodiment is packaged in vacuum and stored at low temperature.
The conductive rubber of the embodiment is liquid conductive rubber, has good fluidity and thixotropy, and has high elasticity and high shielding efficiency after vulcanization. In practical application, the electromagnetic wave isolation device can be applied to the cavity of a 5G base station and terminal products thereof and electromagnetic wave isolation of vehicle-mounted central control equipment, and has a shielding effect of reducing noise by 5-10 dB.
Example 11
1. Conductive rubber composition
The conductive rubber composition of the embodiment comprises the following components in parts by weight: 100 parts of fluorosilicone rubber, 10 parts of carbon nano tubes, 1 part of graphene, 100 parts of M-type nano barium ferrite, 10 parts of vinyltriethoxysilane, and 4 parts of 2, 5-dimethyl-2, 5-bis (tert-butylperoxy) hexane.
2. Conductive rubber
The conductive rubber of the present example was prepared from the above conductive rubber composition.
Specifically, the preparation method of the conductive rubber of the embodiment includes the following steps:
1) mixing the raw materials
Accurately weighing the components in parts by weight, and then placing the components in a mixing roll for mixing; and during mixing, controlling the mixing temperature to be 30 ℃ and the mixing time to be 60-90 min, fully and uniformly dispersing the components, and standing for 8h after sheet discharging to obtain the mixed rubber.
2) Compression molding
And (3) carrying out high-temperature and high-pressure compression molding on the rubber compound by adopting a flat vulcanizing machine. The mold pressing temperature is 150-200 ℃, and the mold pressing pressure is 100-200 MPa.
The conductive rubber can be applied to electronic countermeasure application scenes of weaponry, and achieves an electromagnetic wave attenuation (suppression) effect of 60-100 dB/cm in a wide frequency range of 40 GHz-110 GHz.
Finally, it should be noted that: the above examples are only intended to illustrate the technical solution of the present invention, but not to limit it; although the present invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some technical features may be equivalently replaced; and such modifications or substitutions do not depart from the spirit and scope of the corresponding technical solutions of the embodiments of the present invention.
Claims (10)
1. The conductive rubber composition is characterized by comprising the following components in parts by weight: 100 parts of rubber matrix, 5-30 parts of carbon nano tube, 1-20 parts of graphene, 0-100 parts of barium ferrite, 2-10 parts of silane coupling agent and 1-10 parts of vulcanizing agent.
2. The conductive rubber composition according to claim 1, wherein the rubber matrix is at least one of methyl vinyl silicone rubber, dimethyl silicone rubber, methyl phenyl vinyl silicone rubber, and fluoro silicone rubber.
3. The conductive rubber composition of claim 2, wherein when the rubber matrix is a solid phase rubber matrix, the vulcanizing agent comprises at least one of di-t-butyl peroxide, dicumyl peroxide, 2, 5-dimethyl-2, 5-bis (t-butylperoxy) hexane, and a Pt catalyst.
4. The conductive rubber composition according to claim 2, wherein when the rubber matrix is a liquid phase rubber matrix, the vulcanizing agent includes at least one of methyltriacetoxysilane, methyltriethoxysilane, methyltributanone oxime silane, hexafunctional ethylene siloxane, aniline methyl triethoxysilane, and Pt catalyst.
5. A conductive rubber obtained from the conductive rubber composition according to any one of claims 1 to 4.
6. The conductive rubber according to claim 5, wherein the conductive rubber is used for shielding electromagnetic waves in a frequency range of 1GHz or higher.
7. A method for preparing an electrically conductive rubber, comprising:
placing the rubber matrix, the carbon nano tube, the silane coupling agent, the graphene and the vulcanizing agent in parts by weight into a mixing roll for mixing to obtain a rubber compound, wherein the rubber matrix is a solid phase rubber matrix;
And molding and vulcanizing the rubber compound to obtain the conductive rubber.
8. The method for producing the conductive rubber according to claim 7, wherein the molding and vulcanizing the rubber compound to produce the conductive rubber comprises:
and (2) carrying out compression molding on the mixed rubber by adopting a flat vulcanizing machine, and then carrying out secondary vulcanization to obtain the conductive rubber, wherein the compression molding conditions are as follows: the mold pressing temperature is 150-200 ℃, and the mold pressing pressure is 100-200 MPa.
9. The method for producing the conductive rubber according to claim 7, wherein the molding and vulcanizing the rubber compound to produce the conductive rubber comprises:
and (2) carrying out extrusion molding on the rubber compound by using an extruder, and then carrying out secondary vulcanization to obtain the conductive rubber, wherein the conditions of the extrusion molding are as follows: the extrusion temperature is 200-300 ℃, and the extrusion pressure is 500-1500 PSI.
10. A method for preparing an electrically conductive rubber, comprising:
adding the rubber matrix, the carbon nano tube, the silane coupling agent and the graphene in parts by weight into a stirrer for dispersing and stirring to obtain a semi-finished intermediate adhesive, wherein the rubber matrix is a liquid-phase rubber matrix;
And adding a vulcanizing agent into the semi-finished product intermediate rubber under the conditions of room temperature and vacuum, stirring, and extruding the semi-finished product intermediate rubber added with the vulcanizing agent to obtain the conductive rubber.
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