CN113717532B - Raw material composition, silicone rubber composite material, preparation method and application thereof - Google Patents

Raw material composition, silicone rubber composite material, preparation method and application thereof Download PDF

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CN113717532B
CN113717532B CN202110972801.4A CN202110972801A CN113717532B CN 113717532 B CN113717532 B CN 113717532B CN 202110972801 A CN202110972801 A CN 202110972801A CN 113717532 B CN113717532 B CN 113717532B
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silicone rubber
carbon black
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CN113717532A (en
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李秋影
鲁屹恒
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East China University of Science and Technology
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
    • B29B7/00—Mixing; Kneading
    • B29B7/74—Mixing; Kneading using other mixers or combinations of mixers, e.g. of dissimilar mixers ; Plant
    • B29B7/7476—Systems, i.e. flow charts or diagrams; Plants
    • B29B7/7495—Systems, i.e. flow charts or diagrams; Plants for mixing rubber
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C35/00—Heating, cooling or curing, e.g. crosslinking or vulcanising; Apparatus therefor
    • B29C35/02—Heating or curing, e.g. crosslinking or vulcanizing during moulding, e.g. in a mould
    • C—CHEMISTRY; METALLURGY
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    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/02—Elements
    • C08K3/04—Carbon
    • C08K3/042—Graphene or derivatives, e.g. graphene oxides
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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    • C08K7/00—Use of ingredients characterised by shape
    • C08K7/22—Expanded, porous or hollow particles
    • C08K7/24—Expanded, porous or hollow particles inorganic
    • C08K7/26—Silicon- containing compounds
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    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K9/00—Use of pretreated ingredients
    • C08K9/04—Ingredients treated with organic substances
    • C08K9/06—Ingredients treated with organic substances with silicon-containing compounds
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K9/00—Screening of apparatus or components against electric or magnetic fields
    • H05K9/0073—Shielding materials
    • H05K9/0081—Electromagnetic shielding materials, e.g. EMI, RFI shielding
    • H05K9/0083—Electromagnetic shielding materials, e.g. EMI, RFI shielding comprising electro-conductive non-fibrous particles embedded in an electrically insulating supporting structure, e.g. powder, flakes, whiskers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C08K2003/2265—Oxides; Hydroxides of metals of iron
    • C08K2003/2275—Ferroso-ferric oxide (Fe3O4)
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
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    • C08K2201/002—Physical properties
    • C08K2201/005—Additives being defined by their particle size in general
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    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K2201/00—Specific properties of additives
    • C08K2201/01—Magnetic additives
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K2201/00—Specific properties of additives
    • C08K2201/011—Nanostructured additives

Abstract

The invention discloses a raw material composition, a silicone rubber composite material, a preparation method and an application thereof. Specifically, the raw material composition comprises the following components: silicon rubber, white carbon black and Fe 3 O 4 Graphene, a modifier, a lubricant, and a crosslinking agent; said Fe 3 O 4 Has a median particle diameter of 600-1000nm, and the modifier is hexamethyldisilazane. The silicone rubber composite material prepared from the raw material composition has excellent electromagnetic shielding performance, mechanical property and aging resistance, and the preparation process is simple and is beneficial to industrial production.

Description

Raw material composition, silicone rubber composite material, preparation method and application thereof
Technical Field
The invention relates to a raw material composition, a silicone rubber composite material, a preparation method and application thereof.
Background
With the development and innovation of technology, electromagnetic wave pollution has become a serious threat to human health and ecological environment. To eliminate electromagnetic radiation, researchers choose to shield electromagnetic interference (EMI) with conductive or magnetic materials. The EMI shielding effectiveness of the material includes absorption, reflection and multiple reflections in the shield. Maximizing electromagnetic absorption and converting it into thermal energy is considered to be the most promising and effective solution, and therefore, the design and exploration of electromagnetic absorbing materials with high absorption rate, thinness, and low density is of great scientific interest. Meanwhile, the wave-absorbing composite material not only needs to absorb and attenuate electromagnetic waves, but also needs to consider the using environmental conditions. When the electromagnetic wave absorbing sheet is used for the outer sides of radar, submarine and missile braking areas, the electromagnetic wave absorbing sheet must have good temperature resistance, medium resistance and aging resistance; meanwhile, in precise electronic instruments and medical equipment, the wave-absorbing material with light weight, thin thickness and certain flexibility can meet the requirements.
Chinese patent CN109082123A discloses a preparation method of a graphene modified silicone rubber composite material, which comprises the steps of reacting and uniformly mixing graphene, octamethylcyclotetrasiloxane (D4) and tetramethyltetravinylcyclotetrasiloxane (V4) in the presence of an anionic catalyst, and then adding other auxiliary agents to form the electromagnetic shielding material. Chinese patent CN108165019A discloses a preparation method of a silicone rubber electromagnetic shielding material with a three-dimensional network framework. Chinese patent CN112143236A provides a preparation method of a liquid silicone rubber electromagnetic shielding material, wherein a platinum catalyst is used in part of graphene to introduce double bonds, the double bonds are bonded with hydrogen-containing silicone oil, and the double bonds, the hydrogen-containing silicone oil, the carbon nanotube and aniline jointly act to form a conductive path so as to achieve the electromagnetic shielding effect. Chinese patent CN108977093B provides a preparation method of a flexible silicon rubber wave-absorbing material added with a microstructure interlayer, and the method comprises the steps of penetrating adjacent polyimide films, covering one surface of the polyimide film with a silicon rubber film by using a tape casting or scraping mode, repeatedly covering the other surface with the silicon rubber film, and finally curing to form the flexible wave-absorbing composite material.
Although the above methods can prepare electromagnetic shielding silicone rubber materials, there are some disadvantages: the preparation step uses arylamine reagents, has volatility and toxicity, and is not in accordance with the concept of green chemical development. 2, the composite material only focuses on the electromagnetic shielding performance under low frequency (f is less than 1 GHz), the mechanical properties (tensile strength, hardness, elongation at break and tearing strength) and the environmental resistance are poor, the service life of the material is short, and the material cannot be used for a long time under the severe weather environment. 3, the preparation process is complex in procedure, and the catalyst is expensive, so that the method is not beneficial to industrial production.
Therefore, the research on the silicone rubber composite material which has the electromagnetic shielding performance and stronger mechanical properties (tensile strength, elongation at break and tearing strength), has excellent aging resistance and simple and convenient preparation process and the preparation method thereof have very important scientific research significance and practical significance.
Disclosure of Invention
The invention aims to overcome the defects of poor mechanical property and environmental resistance, short service life and complex preparation process of an electromagnetic shielding silicone rubber material in the prior art, and provides a raw material composition, a silicone rubber composite material, a preparation method and application thereof. The silicone rubber composite material has excellent electromagnetic shielding performance, mechanical property and aging resistance, and the preparation process is simple and is beneficial to industrial production.
The invention solves the technical problems through the following technical scheme:
the invention provides a raw material composition of a silicone rubber composite material, which comprises the following components: silicon rubber, white carbon black and Fe 3 O 4 Graphene, a modifier, a lubricant, and a crosslinker; said Fe 3 O 4 Has a median particle diameter (D50) of 600 to 1000nm, the modifier being Hexamethyldisilazane (HMDS);
wherein, the silicon rubber, the white carbon black and the Fe 3 O 4 The mass ratio of the graphene to the lubricant is 100: (30-50): (1-30): (0.5-2): (1-10), wherein the mass ratio of the modifier to the white carbon black is (15-25): 100, respectively;
the mass ratio of the cross-linking agent to other components is (1-5): 100, and the other components refer to the sum of the components of the raw material composition except the cross-linking agent.
According to the invention, hexamethyldisilazane is used as a modifier of the white carbon black, so that the white carbon black and the silicon rubber are combined more stably, the obtained composite material can keep more stable physical and chemical properties, and the mechanical property is obviously improved.
In one aspect of the present invention, the silicone rubber may be conventional in the art, and preferably, the silicone rubber is a methyl vinyl silicone rubber (e.g., methyl vinyl silicone rubber 110-2), and the vinyl content of the silicone rubber may be 0.1% to 0.2% (e.g., 0.19%).
In one embodiment of the present invention, the silica may be conventional in the art, such as fumed silica or precipitated silica, preferably fumed silica.
In one embodiment of the present invention, the Fe 3 O 4 The median particle diameter (D50) of (A) is preferablyIs 900nm.
In one aspect of the present invention, the graphene may be conventional in the art, and preferably, the graphene is Graphene Nanoplatelets (GNPs), for example, graphene nanoplatelets having a lamella size of about 20-30 μm and a thickness of about 5-8 nm.
In one scheme of the invention, the lubricant is conventional in the field, improves the processability in the mixing process, and can be entangled with silicon-oxygen bonds of silicon rubber to form a stable structure; the performance is kept stable and high temperature resistant during subsequent high temperature flat plate vulcanization. Preferably, the lubricant is Polydimethylsiloxane (PDMS).
In one embodiment of the present invention, the cross-linking agent may be conventional in the art, and preferably, the cross-linking agent is 2,5-dimethyl-2,5-bis (t-butylperoxy) hexane (DBPH).
In one aspect of the present invention, preferably, the mass ratio of the white carbon black to the silicone rubber is (35-45): 100, e.g. 40:100.
in one embodiment of the present invention, preferably, the Fe is Fe 3 O 4 And the mass ratio of the silicon rubber to the silicon rubber is (3-25): 100, e.g. 5, 100, 10:100 or 20:100.
in one aspect of the present invention, preferably, the mass ratio of the graphene to the silicone rubber is (0.8-1.5): 100, e.g. 1.
In one aspect of the present invention, preferably, the mass ratio of the lubricant to the silicone rubber is (2-6): 100, e.g. 4.
In a certain aspect of the present invention, preferably, the mass ratio of the modifier to the white carbon black is (15-20): 100, e.g. 18:100.
in one embodiment of the present invention, the mass ratio of the crosslinking agent to the other components is preferably (1-3): 100, e.g. 2.
In one embodiment of the present invention, the raw material composition consists of the following components: silicon rubber, white carbon black and Fe 3 O 4 Graphene, a modifier, a lubricant, and a crosslinker.
In one embodiment of the present invention, in the raw material composition,silicon rubber, white carbon black and Fe 3 O 4 And the mass ratio of the graphene to the lubricant is 100: (35-45): (3-25): (0.8-1.5): (2-6), the mass ratio of the modifier to the white carbon black is (15-20): 100, the mass ratio of the cross-linking agent to other components is (1-3): 100.
in a certain scheme of the invention, the raw material composition consists of the following components in parts by mass:
Figure BDA0003226508690000041
in a certain scheme of the invention, the raw material composition consists of the following components in parts by mass:
Figure BDA0003226508690000042
in a certain scheme of the invention, the raw material composition consists of the following components in parts by mass:
Figure BDA0003226508690000043
Figure BDA0003226508690000051
the invention also provides a preparation method of the silicone rubber composite material, which adopts the raw material composition as described in any one of the previous items to prepare, and the preparation method comprises the following steps:
(1) Mixing the components except the cross-linking agent in the raw material composition to obtain a rubber compound;
(2) And vulcanizing the rubber compound and a cross-linking agent.
In one embodiment of the present invention, the mixing operation may be a mixing operation conventional in the art. The mixing is generally carried out on an open mill.
In one embodiment of the present invention, the mixing temperature may be conventional in the art, and preferably, the mixing temperature is 60 to 100 ℃, for example, 60 ℃.
In one aspect of the present invention, preferably, the mixing includes the steps of: adding a part of white carbon black, adding silicon rubber, adding the rest white carbon black for several times (such as 2-10 times, and 7 times), adding modifier after each time of adding white carbon black, mixing uniformly, and adding Fe 3 O 4 And graphene, and finally adding a lubricant.
In one embodiment of the present invention, the mixing step preferably further comprises a standing step to remove air bubbles and volatile substances, wherein the temperature of the standing step is preferably 60 to 80 ℃ (for example, 60 ℃), and the time of the standing step is preferably 1.5 to 3 hours (for example, 2 hours).
In one embodiment of the present invention, the vulcanization may be a vulcanization operation that is conventional in the art. Press vulcanization is generally carried out in a hot press.
In one embodiment of the present invention, the temperature of the vulcanization may be conventional in the art, and preferably the temperature of the vulcanization is 160 to 190 ℃, for example 180 ℃.
In one embodiment of the present invention, the time for the vulcanization may be conventional in the art, and preferably, the time for the vulcanization is 10 to 15min, for example, 12min.
In one embodiment of the present invention, the pressure of the vulcanization is conventional in the art, and preferably, the vulcanization pressure is 5-20MPa, for example, pre-pressing at 5-12MPa for 2-8min (for example, pre-pressing at 5MPa for 2 min), and then pressurizing at 10-20MPa for 2-10min (for example, pressurizing at 10MPa for 10 min). Further, in order to fully remove residual gas in the vulcanized rubber, 10-15 times of air exhaust is carried out after pre-pressing and starting pressurization for about 2min.
In one aspect of the present invention, in order to further improve the mechanical properties of the silicone rubber composite material, the method further comprises a secondary vulcanization step after the vulcanization step, wherein the temperature of the secondary vulcanization step is preferably 160 to 220 ℃ (e.g., 200 ℃), and the time of the secondary vulcanization step is preferably 2 to 5 hours (e.g., 4 hours).
The invention also provides a silicone rubber composite material prepared from the raw material composition as described in any one of the preceding items. Preferably, the silicone rubber composite is prepared by the preparation method of the silicone rubber composite as described in any one of the preceding claims.
The invention also provides application of the silicon rubber composite material as an electromagnetic shielding material.
The positive progress effects of the invention are as follows:
(1) The process is simple, the preparation process of simple blending is used, and the performance optimization is realized through the formula and process optimization.
(2) Performing surface hydrophobic modification on white carbon black in a silicon rubber mixing system to avoid agglomeration and improve processing characteristics, and performing electromagnetic absorption on filler (Fe) in a preferred scheme 3 O 4 ) Ball milling is carried out to reduce the particle size, so as to ensure that the maximum electromagnetic wave reflection loss is obtained while maintaining excellent mechanical properties.
(3) The silicon rubber wave-absorbing composite material has electromagnetic shielding performance (particularly good wave-absorbing performance at high frequency), excellent mechanical property and durability, and through formula and process optimization, the absolute value of reflection loss of electromagnetic waves in a range of 2-18GHz is more than 10dB (loss of the electromagnetic waves is more than 90%) while the silicon rubber composite material is endowed with excellent mechanical property (high tensile strength, high elongation at break, high tear strength and low hardness), and in addition, the heat-resistant air and the humidity-resistant environment aging performance are kept good.
Drawings
FIG. 1 shows the reflection loss RL of examples 1 to 3 and comparative example 1 in the frequency band of 2 to 18GHz with a thickness of 1.7mm.
Detailed Description
The invention is further illustrated by the following examples, which are not intended to limit the invention thereto.
Example 1
For magnetic filler Fe 3 O 4 Carrying out ball milling: firstly Fe 3 O 4 The microspheres are precisely weighed and put into a 240-revolution/min ball mill (XDQM variable speed planetary ball mill) for ball milling for 3 hours at room temperature, wherein the grinding balls/Fe 3 O 4 Microsphere mass ratio 6:1, grinding ball (zirconia) pellet (straight)The mass ratio of the diameter of 3mm to the large ball (the diameter of 6 mm) is 1:1, the test is carried out by a laser particle size analyzer, and the Fe after ball milling is carried out 3 O 4 Has a particle diameter of about 900nm.
The three-section temperature of the torque rheometer is set to be 60 ℃, and the rotating speed of the rotor is 25r/min. Adding 2g of fumed silica into a mold cavity, sequentially adding 110-2 parts (the vinyl content is 0.19 percent, the total content is 40 g) of methyl vinyl silicone rubber, fully mixing for 3min, adding 7 times of fumed silica (the total content is 16 g) and dropwise adding Hexamethyldisilazane (HMDS) (each time 0.41g, the total content is 2.88g, the mass is 18 percent of the mass of the white carbon black), fully mixing until powder white carbon black cannot be seen, and sequentially adding a magnetic filler Fe subjected to ball milling into the mixture until the magnetic filler Fe subjected to ball milling is completely mixed with the powder white carbon black 3 O 4 Adding particles (2 g, 900nm, D50), and mixing for 2-3min; and then adding graphene nano-sheets GNP (0.4 g, the layer size is about 20-30 mu m, and the thickness is about 5-8 nm) for 2-3 times, mixing for 3min, then dropwise adding PDMS (1.6 g), waiting for the torque of the rubber compound to be stabilized at 6.0-6.5 dN.m, mixing for 5min, stopping the machine for collection, placing the mixture in an oven at 60 ℃ for 2h, weighing, then adding 2,5-dimethyl-2,5-Dihexane (DBPH) (1.25 g, the mass is 2% of the total mass of the rubber compound) in an open mill, vulcanizing, rolling, packaging, and thinly passing for several times, and placing the sheets in a sealing bag for storage. Then putting the mixture into a hot press at 180 ℃ for flat vulcanization. Pre-pressing for 2min at 5MPa, exhausting 15 times after pre-pressing, pressurizing for 2min at 10-20MPa, exhausting 5-10 times, pressurizing for 8min at 10MPa, cooling to 25 deg.C, demolding, collecting, and storing in packaging bag.
Then placing the mixture in a blast oven at 200 ℃ for 4h for secondary vulcanization. The prepared wave-absorbing rubber sheet has the length of 100mm, the width of 100mm and the thickness of 1.7mm.
Example 2
The three-section temperature of the torque rheometer is set to be 60 ℃, and the rotating speed of the rotor is 25r/min. 2g of fumed silica is added into a mold cavity, then methyl vinyl silicone rubber 110-2 (vinyl content 0.19%, total 40 g) is added in sequence, after fully mixing for 3min, fumed silica (total 16 g) is added in 7 times and Hexamethyldisilazane (HMDS) is added dropwise (0.41 g each time, total 2.88 g)g, the mass is 18 percent of the mass of the white carbon black), and the magnetic fillers Fe after ball milling are added in sequence when the white carbon black powder can not be seen 3 O 4 Adding particles (4 g, 900nm, D50), and mixing for 2-3min; then adding GNP (0.4 g) for 2-3 times, mixing for 3min, dropwise adding PDMS (1.6 g), waiting for the torque of the rubber compound to be stabilized at 6.0-6.5 dN.m, mixing for 5min, stopping the machine, collecting, placing in an oven at 60 ℃ for 2h, weighing, adding 2,5-dimethyl-2,5-Dihexyl (DBPH) (1.29 g, the mass is 2% of the total mass of the rubber compound) in an open mill, vulcanizing, rolling, packaging, thinly passing for several times, placing in a sealing bag for storage after sheet discharging. Then putting the mixture into a hot press at 180 ℃ for flat vulcanization. Pre-pressing for 2min at 5MPa, exhausting 15 times after pre-pressing, pressurizing for 2min at 10MPa, exhausting 5-10 times, pressurizing for 8min at 10-20MPa, cooling to 25 deg.C, demolding, collecting, and storing in packaging bag.
Then placing the mixture in a blast oven at 200 ℃ for 4h for secondary vulcanization. The prepared wave-absorbing rubber sheet has the length of 100mm, the width of 100mm and the thickness of 1.7mm.
Example 3
The three-section temperature of the torque rheometer is set to be 60 ℃, and the rotating speed of the rotor is 25r/min. Adding 2g of fumed silica into a mold cavity, sequentially adding 110-2 parts (the vinyl content is 0.19 percent, the total content is 40 g) of methyl vinyl silicone rubber, fully mixing for 3min, adding 7 times of fumed silica (the total content is 16 g) and dropwise adding Hexamethyldisilazane (HMDS) (each time 0.41g, the total content is 2.88g, the mass is 18 percent of the mass of the white carbon black), fully mixing until powder white carbon black cannot be seen, and sequentially adding a magnetic filler Fe subjected to ball milling into the mixture until the magnetic filler Fe subjected to ball milling is completely mixed with the powder white carbon black 3 O 4 Adding 8g of granules (900nm and D50) and mixing for 2-3min; adding GNP (0.4 g) 2-3 times, mixing for 3min, adding PDMS (1.6 g) dropwise, waiting for the torque of the rubber compound to be stabilized at 6.0-6.5 dN.m, mixing for 5min, stopping the machine, collecting, placing in an oven at 60 deg.C for 2h, weighing, adding 2,5-dimethyl-2,5-Dihexyl (DBPH) (1.37 g, mass is 2% of the total mass of the rubber compound), vulcanizing, rolling, packaging, and passing for several times to obtain the final productAnd then the mixture is placed in a packaging bag for storage. Then putting the mixture into a hot press at 180 ℃ for flat vulcanization. Pre-pressing for 2min at 5MPa, exhausting 15 times after pre-pressing, pressurizing for 2min at 10MPa, exhausting 5-10 times, pressurizing for 8min at 10-20MPa, cooling to 25 deg.C, demolding, collecting, and storing in packaging bag.
Then placing the mixture in a blast oven at 200 ℃ for 4h for secondary vulcanization. The prepared wave-absorbing rubber sheet has the length of 100mm, the width of 100mm and the thickness of 1.7mm.
Comparative example 1
The three-section temperature of the torque rheometer is set to be 60 ℃, and the rotating speed of the rotor is 25r/min. Adding 2g of fumed silica into a mold cavity, sequentially adding 110-2 parts (the vinyl content is 0.19 percent, the total content is 40 g) of methyl vinyl silicone rubber, fully mixing for 3min, adding 7 times of fumed silica (the total content is 16 g) and dropwise adding Hexamethyldisilazane (HMDS) (each time 0.41g, the total content is 2.88g, the mass is 18 percent of the mass of the white carbon black), fully mixing until powder white carbon black cannot be seen, and sequentially adding a magnetic filler Fe subjected to ball milling into the mixture until the magnetic filler Fe subjected to ball milling is completely mixed with the powder white carbon black 3 O 4 Adding particles (4 g, 900nm, D50), and mixing for 2-3min; then adding CCNT (0.4 g, conductive carbon nano tube, the diameter is 10-25nm, the average diameter is 20 nm) in 2-3 times, mixing for 3min, adding PDMS (1.6 g) dropwise, waiting for the torque of the mixed rubber to be stabilized at 5.0-5.5 dN.m (because the comparative example can not reach 6.0 dN.m), mixing for 5min, stopping, collecting, placing in an oven at 60 ℃ for 2h, weighing, adding 2,5-dimethyl-2,5-Dihexyl (DBPH) (1.29 g, the mass is 2% of the total mass of the mixed rubber) in an open mill, vulcanizing, rolling, packaging, thinly passing for several times, placing pieces, and storing in a sealing bag. Then putting the mixture into a hot press at 180 ℃ for flat vulcanization. Pre-pressing for 2min at 5MPa, exhausting 15 times after pre-pressing, pressurizing for 2min at 10MPa, exhausting 5-10 times, pressurizing for 8min at 10-20MPa, cooling to 25 deg.C, demolding, collecting, and storing in packaging bag.
Then placing the mixture in a blast oven at 200 ℃ for 4h for secondary vulcanization. The prepared wave-absorbing rubber sheet has the length of 100mm, the width of 100mm and the thickness of 1.7mm.
Comparative example 2 (without modifier)
The three-section temperature of the torque rheometer is set to be 60 ℃, and the rotating speed of the rotor is 25r/min. Adding 2g of fumed silica into a mold cavity, sequentially adding 110-2 parts (the vinyl content is 0.19 percent, the total weight is 40 g) of methyl vinyl silicone rubber, fully mixing for 3min, adding 7-10 times of fumed silica (the total weight is 16 g), fully mixing until no powdery silica can be seen, and sequentially adding the magnetic filler Fe subjected to ball milling until no powdery silica is seen 3 O 4 Adding particles (2 g, 900nm, D50), and mixing for 2-3min; adding GNP (0.4 g) for 2-3 times, mixing for 3min, adding PDMS (1.6 g) dropwise, waiting until the torque of the rubber compound is stabilized at 4-4.5 dN.m, mixing for 5min, stopping the machine, collecting, placing in an oven at 60 deg.C for 2h, weighing, adding 2,5-dimethyl-2,5-Dihexyl (DBPH) (the mass is 2% of the total mass of the rubber compound) in an open mill, vulcanizing, rolling, packaging, thinly passing for several times, and placing in a sealed bag for storage. Then putting the mixture into a hot press at 180 ℃ for flat vulcanization. Pre-pressing for 2min at 5MPa, exhausting 15 times after pre-pressing, pressurizing for 2min at 10-20MPa, exhausting 5-10 times, pressurizing for 8min at 10MPa, cooling to 25 deg.C, demolding, collecting, and storing in packaging bag.
Then placing the mixture in a blast oven at 200 ℃ for 4h for secondary vulcanization. The prepared wave-absorbing rubber sheet has the length of 100mm, the width of 100mm and the thickness of 1.7mm.
Comparative example 3 (without modifier)
The three-section temperature of the torque rheometer is set to be 60 ℃, and the rotating speed of the rotor is 25r/min. Adding 2g of fumed silica into a mold cavity, sequentially adding 110-2 parts (the vinyl content is 0.19 percent, the total weight is 40 g) of methyl vinyl silicone rubber, fully mixing for 3min, adding 7-10 times of fumed silica (the total weight is 16 g), fully mixing until powder white carbon black can not be seen, and sequentially adding the magnetic filler Fe subjected to ball milling 3 O 4 Adding particles (4 g, 900nm, D50), and mixing for 2-3min; GNP (0.4 g) was then added in 2-3 portions, mixed for 3min and PDMS (1.6 g) was added dropwise, waiting for the mix to be clearStabilizing the torque at 4-4.5 dN.m, mixing for 5min, stopping the machine, collecting, placing in an oven at 60 ℃ for 2h, weighing, adding 2,5-dimethyl-2,5-Dihexyl (DBPH) (the mass is 2% of the total mass of the rubber compound) into an open mill, vulcanizing, rolling, packaging, thinly passing for several times, discharging, and placing in a packaging bag for storage. Then putting the mixture into a hot press at 180 ℃ for flat vulcanization. Pre-pressing for 2min at 5MPa, exhausting 15 times after pre-pressing, pressurizing for 2min at 10-20MPa, exhausting 5-10 times, pressurizing for 8min at 10MPa, cooling to 25 deg.C, demolding, collecting, and storing in packaging bag.
Then placing the mixture in a blast oven at 200 ℃ for 4h for secondary vulcanization. The prepared wave-absorbing rubber sheet has the length of 100mm, the width of 100mm and the thickness of 1.7mm.
Comparative example 4 (without modifier)
The three-stage temperature of the torque rheometer is set to be 60 ℃, and the rotating speed of the rotor is 25r/min. Adding 2g of fumed silica into a mold cavity, sequentially adding 110-2 parts (the vinyl content is 0.19 percent, the total weight is 40 g) of methyl vinyl silicone rubber, fully mixing for 3min, adding 7-10 times of fumed silica (the total weight is 16 g), fully mixing until powder white carbon black can not be seen, and sequentially adding the magnetic filler Fe subjected to ball milling 3 O 4 Adding 8g of granules (900nm and D50) and mixing for 2-3min; adding GNP (0.4 g) for 2-3 times, mixing for 3min, adding PDMS (1.6 g) dropwise, waiting until the torque of the rubber compound is stabilized at 4-4.5 dN.m, mixing for 5min, stopping the machine, collecting, placing in an oven at 60 deg.C for 2h, weighing, adding 2,5-dimethyl-2,5-Dihexyl (DBPH) (the mass is 2% of the total mass of the rubber compound) in an open mill, vulcanizing, rolling, packaging, thinly passing for several times, and placing in a sealed bag for storage. Then putting the mixture into a hot press at 180 ℃ for flat vulcanization. Pre-pressing for 2min at 5MPa, exhausting 15 times after pre-pressing, pressurizing for 2min at 10-20MPa, exhausting 5-10 times, pressurizing for 8min at 10MPa, cooling to 25 deg.C, demolding, collecting, and storing in packaging bag.
Then placing the mixture in a blast oven at 200 ℃ for 4h for secondary vulcanization. The prepared wave-absorbing rubber sheet has the length of 100mm, the width of 100mm and the thickness of 1.7mm.
Comparative example 5 (no modifier and Fe added) 3 O 4 )
The three-section temperature of the torque rheometer is set to be 60 ℃, and the rotating speed of the rotor is 25r/min. Adding 2g of fumed silica into a mold cavity, sequentially adding 110-2 parts of methyl vinyl silicone rubber (the vinyl content is 0.19 percent, and the total content is 40 g), fully mixing for 3min, adding 7-10 times of fumed silica (the total content is 16 g), fully mixing, adding 2-3 times of GNP (0.4 g), mixing for 3min, dropwise adding PDMS (1.6 g), waiting until the torque of the rubber compound is stabilized at 4-4.5 dN.m, mixing for 5min, stopping the machine, collecting, placing in an oven at 60 ℃ for 2h, weighing, adding 2,5-dimethyl-2,5-Dihexyl (DBPH) (the mass is 2 percent of the total mass of the rubber compound) in an open mill, vulcanizing, rolling, packaging, thinly passing for several times, placing sheets in a sealing bag, and storing. Then putting the mixture into a hot press at 180 ℃ for flat vulcanization. Pre-pressing for 2min at 5MPa, exhausting 15 times after pre-pressing, pressurizing for 2min at 10-20MPa, exhausting 5-10 times, pressurizing for 8min at 10MPa, cooling to 25 deg.C, demolding, collecting, and storing in packaging bag.
Then placing the mixture in a blast oven at 200 ℃ for 4h for secondary vulcanization. The prepared wave-absorbing rubber sheet has the length of 100mm, the width of 100mm and the thickness of 1.7mm.
Comparative example 6 (using KH570 as modifier)
The three-section temperature of the torque rheometer is set to be 60 ℃, and the rotating speed of the rotor is 25r/min. Adding 2g of fumed silica into a mold cavity, sequentially adding 110-2 parts (the vinyl content is 0.19 percent, the total weight is 40 g) of methyl vinyl silicone rubber, fully mixing for 3min, adding 7-10 times of fumed silica (the total weight is 16 g), fully mixing until powder white carbon black can not be seen, and sequentially adding the magnetic filler Fe subjected to ball milling 3 O 4 Adding particles (2 g, 900nm, D50), and mixing for 2-3min; then adding GNP (0.4 g) in 2-3 times, mixing for 3min, adding silane coupling agent KH570 (0.8 g) dropwise, mixing for 2-3min, adding PDMS (1.6 g) dropwise, waiting for the torque of the rubber mixture to stabilize at 4.5-5.0 dN.m,mixing for 5min, stopping the machine, collecting, placing in an oven at 60 deg.C for 2h, weighing, adding 2,5-dimethyl-2,5-Dihexyl (DBPH) (the mass is 2% of the total mass of the rubber compound) in an open mill, vulcanizing, rolling, packaging, thinly passing for several times, discharging, and storing in a packaging bag. Then putting the mixture into a hot press at 180 ℃ for flat vulcanization. Pre-pressing for 2min at 5MPa, exhausting 15 times after pre-pressing, pressurizing for 2min at 10-20MPa, exhausting 5-10 times, pressurizing for 8min at 10MPa, cooling to 25 deg.C, demolding, collecting, and storing in packaging bag.
Then placing the mixture in a blast oven at 200 ℃ for 4h for secondary vulcanization. The prepared wave-absorbing rubber sheet has the length of 100mm, the width of 100mm and the thickness of 1.7mm.
Comparative example 7 (using KH570 as modifier)
The three-section temperature of the torque rheometer is set to be 60 ℃, and the rotating speed of the rotor is 25r/min. Adding 2g of fumed silica into a mold cavity, sequentially adding 110-2 parts (the vinyl content is 0.19 percent, the total content is 40 g) of methyl vinyl silicone rubber, fully mixing for 3min, adding 7-10 times of fumed silica (the total content is 16 g), fully mixing until no powdery silica can be seen, sequentially adding 4g of magnetic filler Fe3O4 particles (the particle size is 900nm, and the particle size is D50) after ball milling, and fully mixing for 2-3min after each addition; then adding GNP (0.4 g) for 2-3 times, mixing for 3min, dropwise adding a silane coupling agent KH570 (0.8 g), mixing for 2-3min, dropwise adding PDMS (1.6 g), waiting for the torque of the mixed rubber to be 4.5-5.0 dN.m, mixing for 5min, stopping the machine, collecting, placing in an oven at 60 ℃ for 2h, weighing, adding 2,5-dimethyl-2,5-Dihexyl (DBPH) (the mass is 2% of the total mass of the mixed rubber), vulcanizing, rolling, packaging, and thinly passing for several times, placing in a sealing bag for storage after sheet discharging. Then putting the mixture into a hot press at 180 ℃ for flat vulcanization. Pre-pressing for 2min at 5MPa, exhausting 15 times after pre-pressing, pressurizing for 2min at 10-20MPa, exhausting 5-10 times, pressurizing for 8min at 10MPa, cooling to 25 deg.C, demolding, collecting, and storing in packaging bag.
Then placing the mixture in a blast oven at 200 ℃ for 4h for secondary vulcanization. The prepared wave-absorbing rubber sheet has the length of 100mm, the width of 100mm and the thickness of 1.7mm.
Comparative example 8 (using KH570 as modifier)
The three-section temperature of the torque rheometer is set to be 60 ℃, and the rotating speed of the rotor is 25r/min. Adding 2g of fumed silica into a mold cavity, sequentially adding 110-2 parts (the vinyl content is 0.19 percent, the total content is 40 g) of methyl vinyl silicone rubber, fully mixing for 3min, adding 7-10 times of fumed silica (the total content is 16 g), fully mixing until no powdery silica can be seen, sequentially adding 8g of magnetic filler Fe3O4 particles (the particle size is 900nm, and the particle size is D50) after ball milling, and fully mixing for 2-3min after each addition; then adding GNP (0.4 g) for 2-3 times, mixing for 3min, dropwise adding a silane coupling agent KH570 (0.8 g), mixing for 2-3min, dropwise adding PDMS (1.6 g), waiting for the torque of the mixed rubber to be 4.5-5.0 dN.m, mixing for 5min, stopping the machine, collecting, placing in an oven at 60 ℃ for 2h, weighing, adding 2,5-dimethyl-2,5-Dihexyl (DBPH) (the mass is 2% of the total mass of the mixed rubber), vulcanizing, rolling, packaging, and thinly passing for several times, placing in a sealing bag for storage after sheet discharging. Then putting the mixture into a hot press at 180 ℃ for flat vulcanization. Pre-pressing for 2min at 5MPa, exhausting 15 times after pre-pressing, pressurizing for 2min at 10-20MPa, exhausting 5-10 times, pressurizing for 8min at 10MPa, cooling to 25 deg.C, demolding, collecting, and storing in packaging bag.
Then placing the mixture in a blast oven at 200 ℃ for 4h for secondary vulcanization. The prepared wave-absorbing rubber sheet has the length of 100mm, the width of 100mm and the thickness of 1.7mm.
Comparative example 9 (using KH570 as modifier, without Fe addition) 3 O 4 )
The three-stage temperature of the torque rheometer is set to be 60 ℃, and the rotating speed of the rotor is 25r/min. Adding 2g of fumed silica into a mold cavity, sequentially adding 110-2 parts of methyl vinyl silicone rubber (the vinyl content is 0.19 percent, the total content is 40 g), fully mixing for 3min, adding 7-10 parts of fumed silica (the total content is 16 g), fully mixing, adding 2-3 parts of GNP (0.4 g), mixing for 3min, dropwise adding a silane coupling agent KH570 (0.8 g), mixing for 2-3min, dropwise adding PDMS (1.6 g), mixing for 5min, stopping the machine for collection, placing the mixture in an oven for 2h at 60 ℃, weighing, and adding 2,5-dimethyl-2,5-Dihexyl (DBPH) (the mass is 2 percent of the total mass of the mixed rubber) into an open mill. Sulfurizing, rolling, packing, passing through for several times, discharging, and storing in sealed bag. Then putting the mixture into a hot press at 180 ℃ for flat vulcanization. Pre-pressing for 2min at 5MPa, exhausting 15 times after pre-pressing, pressurizing for 2min at 10-20MPa, exhausting 5-10 times, pressurizing for 8min at 10MPa, cooling to 25 deg.C, demolding, collecting, and storing in packaging bag.
Then placing the mixture in a blast oven at 200 ℃ for 4h for secondary vulcanization. The prepared wave-absorbing rubber sheet has the length of 100mm, the width of 100mm and the thickness of 1.7mm.
Comparative example 10 (using KH151 as modifier)
The three-section temperature of the torque rheometer is set to be 60 ℃, and the rotating speed of the rotor is 25r/min. Adding 2g of fumed silica into a mold cavity, sequentially adding 110-2 parts (the vinyl content is 0.19 percent, and the total content is 40 g) of methyl vinyl silicone rubber, fully mixing for 3min, adding 7-10 times of fumed silica (the total content is 16 g), fully mixing until powdery silica cannot be seen, sequentially adding 2g of magnetic filler Fe3O4 particles (the particle size is 900nm and D50) after ball milling, and fully mixing for 2-3min after each addition; then adding GNP (0.4 g) for 2-3 times, mixing for 3min, dropwise adding silane coupling agent KH151 (0.8 g), mixing for 2-3min, dropwise adding PDMS (1.6 g), waiting for the torque of the mixed rubber to be 4.5-5.0 dN.m, mixing for 5min, stopping the machine, collecting, placing in an oven at 60 deg.C for 2h, weighing, adding 2,5-dimethyl-2,5-Dihexyl (DBPH) (the mass is 2% of the total mass of the mixed rubber), vulcanizing, rolling, packaging, and thinly passing for several times, placing in a sealed bag for storage after sheet discharging. Then putting the mixture into a hot press at 180 ℃ for flat vulcanization. Pre-pressing for 2min at 5MPa, exhausting 15 times after pre-pressing, pressurizing for 2min at 10-20MPa, exhausting 5-10 times, pressurizing for 8min at 10MPa, cooling to 25 deg.C, demolding, collecting, and storing in packaging bag.
Then placing the mixture in a blast oven at 200 ℃ for 4h for secondary vulcanization. The prepared wave-absorbing rubber sheet has the length of 100mm, the width of 100mm and the thickness of 1.7mm.
Comparative example 11 (using KH151 as modifier)
The three-section temperature of the torque rheometer is set to be 60 ℃, and the rotating speed of the rotor is 25r/min. Adding 2g of fumed silica into a mold cavity, sequentially adding 110-2 parts (the vinyl content is 0.19 percent, the total content is 40 g) of methyl vinyl silicone rubber, fully mixing for 3min, adding 7-10 times of fumed silica (the total content is 16 g), fully mixing until no powdery silica can be seen, sequentially adding 4g of magnetic filler Fe3O4 particles (the particle size is 900nm, and the particle size is D50) after ball milling, and fully mixing for 2-3min after each addition; then adding GNP (0.4 g) for 2-3 times, mixing for 3min, dropwise adding a silane coupling agent KH151 (0.8 g), mixing for 2-3min, dropwise adding PDMS (1.6 g), waiting for the torque of the rubber compound to be stabilized at 4.5-5.0 dN.m, further mixing for 5min, stopping the machine for collection, placing the rubber compound in an oven at 60 ℃ for 2h, weighing, adding 2,5-dimethyl-2,5-Dihexane (DBPH) (the mass is 2% of the total mass of the rubber compound) in an open mill, packing, vulcanizing, rolling, thinly passing for several times, placing pieces, and storing in a sealed bag. Then putting the mixture into a hot press at 180 ℃ for flat vulcanization. Pre-pressing for 2min at 5MPa, exhausting 15 times after pre-pressing, pressurizing for 2min at 10-20MPa, exhausting 5-10 times, pressurizing for 8min at 10MPa, cooling to 25 deg.C, demolding, collecting, and storing in packaging bag.
Then placing the mixture in a blast oven at 200 ℃ for 4h for secondary vulcanization. The prepared wave-absorbing rubber sheet has the length of 100mm, the width of 100mm and the thickness of 1.7mm.
Comparative example 12 (using KH151 as modifier)
The three-section temperature of the torque rheometer is set to be 60 ℃, and the rotating speed of the rotor is 25r/min. Adding 2g of fumed silica into a mold cavity, sequentially adding 110-2 parts (the vinyl content is 0.19 percent, the total content is 40 g) of methyl vinyl silicone rubber, fully mixing for 3min, adding 7-10 times of fumed silica (the total content is 16 g), fully mixing until no powdery silica can be seen, sequentially adding 8g of magnetic filler Fe3O4 particles (the particle size is 900nm, and the particle size is D50) after ball milling, and fully mixing for 2-3min after each addition; then adding GNP (0.4 g) for 2-3 times, mixing for 3min, dropwise adding silane coupling agent KH151 (0.8 g), mixing for 2-3min, dropwise adding PDMS (1.6 g), waiting for the torque of the mixed rubber to be 4.5-5.0 dN.m, mixing for 5min, stopping the machine, collecting, placing in an oven at 60 deg.C for 2h, weighing, adding 2,5-dimethyl-2,5-Dihexyl (DBPH) (the mass is 2% of the total mass of the mixed rubber), vulcanizing, rolling, packaging, and thinly passing for several times, placing in a sealed bag for storage after sheet discharging. Then putting the mixture into a hot press at 180 ℃ for flat vulcanization. Pre-pressing for 2min at 5MPa, exhausting 15 times after pre-pressing, pressurizing for 2min at 10-20MPa, exhausting 5-10 times, pressurizing for 8min at 10MPa, cooling to 25 deg.C, demolding, collecting, and storing in packaging bag.
Then placing the mixture in a blast oven at 200 ℃ for 4h for secondary vulcanization. The prepared wave-absorbing rubber sheet has the length of 100mm, the width of 100mm and the thickness of 1.7mm.
Comparative example 13 (using KH151 as modifier, without addition of Fe 3 O 4 )
The three-section temperature of the torque rheometer is set to be 60 ℃, and the rotating speed of the rotor is 25r/min. Adding 2g of fumed silica into a mold cavity, sequentially adding 110-2 parts of methyl vinyl silicone rubber (the vinyl content is 0.19 percent, the total content is 40 g), fully mixing for 3min, adding 7-10 parts of fumed silica (the total content is 16 g), fully mixing, adding 2-3 parts of GNP (0.4 g), mixing for 3min, dropwise adding a silane coupling agent KH151 (0.8 g), mixing for 2-3min, dropwise adding PDMS (1.6 g), mixing for 5min, stopping the machine for collection, placing the mixture in an oven for 2h at 60 ℃, weighing, and adding 2,5-dimethyl-2,5-Dihexyl (DBPH) (the mass is 2 percent of the total mass of the mixed rubber) into an open mill. Sulfurizing, rolling, packing, passing through for several times, discharging, and storing in sealed bag. Then putting the mixture into a hot press at 180 ℃ for flat vulcanization. Pre-pressing for 2min at 5MPa, exhausting 15 times after pre-pressing, pressurizing for 2min at 10-20MPa, exhausting 5-10 times, pressurizing for 8min at 10MPa, cooling to 25 deg.C, demolding, collecting, and storing in packaging bag.
Then placing the mixture in a blast oven at 200 ℃ for 4h for secondary vulcanization. The prepared wave-absorbing rubber sheet has the length of 100mm, the width of 100mm and the thickness of 1.7mm.
Comparative example 14
The three-section temperature of the torque rheometer is set to be 60 ℃, and the rotating speed of the rotor is 25r/min. Adding 2g of fumed silica into a mold cavity, sequentially adding 110-2 parts of methylvinyl silicone rubber (the vinyl content is 0.19 percent, and the total content is 40 g), fully mixing for 3min, adding 7 times of fumed silica (the total content is 16 g) and dropwise adding Hexamethyldisilazane (HMDS) (0.41 g and the total content is 2.88g, and the mass of HMDS) until 18 percent of powdery silica cannot be seen, fully mixing until non-ball-milled magnetic filler Fe is sequentially added 3 O 4 Adding granule (2 g, with particle diameter of 1300nm, D50) each time, and mixing for 2-3min; then adding GNP (0.4 g) 2-3 times, mixing for 3min, dropwise adding PDMS (1.6 g), waiting until the torque of the rubber compound is stabilized at 6.0-6.5 dN.m, mixing for 5min, stopping the machine, collecting, placing in an oven at 60 deg.C for 2h, weighing, adding 2,5-dimethyl-2,5-Dihexyl (DBPH) (1.29 g, the mass is 2% of the total mass of the rubber compound) in an open mill, vulcanizing, rolling, packaging, thinly passing for several times, and placing in a sealed bag for storage after sheet discharging. Then putting the mixture into a hot press at 180 ℃ for flat vulcanization. Pre-pressing for 2min at 5MPa, exhausting 15 times after pre-pressing, pressurizing for 2min at 10MPa, exhausting 5-10 times, pressurizing for 8min at 10-20MPa, cooling to 25 deg.C, demolding, collecting, and storing in packaging bag.
Then placing the mixture in a blast oven at 200 ℃ for 4h for secondary vulcanization. The prepared wave-absorbing rubber sheet has the length of 100mm, the width of 100mm and the thickness of 1.7mm.
Comparative example 15
The three-section temperature of the torque rheometer is set to be 60 ℃, and the rotating speed of the rotor is 25r/min. Adding 2g of fumed silica into a mold cavity, sequentially adding 110-2 (vinyl content is 0.19%, total amount is 40 g) of methyl vinyl silicone rubber, mixing for 3min, and dividing into 7 partsAdding gas phase white carbon black (total 16 g) and adding Hexamethyldisilazane (HMDS) dropwise (each time adding 0.41g, total 2.88g, mass is 18% of white carbon black mass), mixing thoroughly until no powder white carbon black is seen, adding non-ball-milled magnetic filler Fe 3 O 4 Adding granules (4 g, with particle diameter of 1300nm and D50), and mixing for 2-3min; then adding GNP (0.4 g) 2-3 times, mixing for 3min, dropwise adding PDMS (1.6 g), waiting until the torque of the rubber compound is stabilized at 6.0-6.5 dN.m, mixing for 5min, stopping the machine, collecting, placing in an oven at 60 deg.C for 2h, weighing, adding 2,5-dimethyl-2,5-Dihexyl (DBPH) (1.29 g, the mass is 2% of the total mass of the rubber compound) in an open mill, vulcanizing, rolling, packaging, thinly passing for several times, and placing in a sealed bag for storage after sheet discharging. Then putting the mixture into a hot press at 180 ℃ for flat vulcanization. Pre-pressing for 2min at 5MPa, exhausting 15 times after pre-pressing, pressurizing for 2min at 10MPa, exhausting 5-10 times, pressurizing for 8min at 10-20MPa, cooling to 25 deg.C, demolding, collecting, and storing in packaging bag.
Then placing the mixture in a blast oven at 200 ℃ for 4h for secondary vulcanization. The prepared wave-absorbing rubber sheet has the length of 100mm, the width of 100mm and the thickness of 1.7mm.
Comparative example 16
The three-stage temperature of the torque rheometer is set to be 60 ℃, and the rotating speed of the rotor is 25r/min. Adding 2g of fumed silica into a mold cavity, sequentially adding 110-2 parts (the vinyl content is 0.19 percent, the total content is 40 g) of methyl vinyl silicone rubber, fully mixing for 3min, adding 7 times of fumed silica (the total content is 16 g) and dropwise adding Hexamethyldisilazane (HMDS) (each time 0.41g, the total content is 2.88g, the mass is 18 percent of the mass of the white carbon black), fully mixing until powder white carbon black can not be seen, and sequentially adding non-ball-milled magnetic filler Fe 3 O 4 Adding granules (8 g, with particle diameter of 1300nm and D50), and mixing for 2-3min; adding GNP (0.4 g) 2-3 times, mixing for 3min, adding PDMS (1.6 g) dropwise, waiting until the torque of the rubber compound is stabilized at 6.0-6.5 dN.m, mixing for 5min, stopping the machine, collecting, placing in an oven at 60 deg.C for 2h, weighing, adding 2,5-dimethyl-2,5-dihexyl in an open millAnd (3) vulcanizing alkane (DBPH) (1.29 g, the mass is 2 percent of the total mass of the rubber compound), rolling, packing, thinly passing for a plurality of times, discharging, and storing in a packaging bag. Then putting the mixture into a hot press at 180 ℃ for flat vulcanization. Pre-pressing for 2min at 5MPa, exhausting 15 times after pre-pressing, pressurizing for 2min at 10MPa, exhausting 5-10 times, pressurizing for 8min at 10-20MPa, cooling to 25 deg.C, demolding, collecting, and storing in packaging bag.
Then placing the mixture in a blast oven at 200 ℃ for 4h for secondary vulcanization. The prepared wave-absorbing rubber sheet has the length of 100mm, the width of 100mm and the thickness of 1.7mm.
Performance testing
(1) Mechanical properties were measured for examples 1 to 3, comparative examples 1 to 16 and pure vulcanized silicone rubber (available from Dongjue Silicone group Co., ltd., vinyl molar mass 0.19%). The vulcanized sample was cut into a dumbbell shape (standard of GB/T528-2009 dumbbell rubber sample), a tear square shape (standard of GB/T529-2008 tear strength (right angle)), and a circular ring shape having an inner diameter of 3.00mm, an outer diameter of 6.95mm, and a thickness of 1.7mm, and the tensile strength, elongation at break, tear strength (right angle), and electromagnetic absorption property were respectively tested at a tensile speed of 500 mm/min. In addition, the vulcanizate was tested for shore a hardness with a durometer. And (3) carrying out the test of the electromagnetic wave reflection loss in the range of 2-18GHz by using a vector network analyzer.
The results are shown in table 1 and fig. 1.
TABLE 1 vulcanizate tensile, tear strength (Right Angle), hardness and maximum vertical Reflection Loss (RL)
Figure BDA0003226508690000201
From the above table, it can be seen that the pure silicone rubber has very poor tensile properties and tear strength, and has no application value for long-term use. With magnetic filler Fe 3 O 4 The content is increased, the tensile strength and the tearing strength of the samples of the examples 1 to 3 are fluctuated, the tensile strength is more than 5.30MPa, the maximum tensile strength can reach 6.30MPa, and the elongation at break isThe elongation is always stabilized between 370 and 385%, the tear strength (right angle) is maintained between 8 and 12kN/m, and the Shore A hardness is less than 50 degrees. In addition, the maximum value of the vertical reflection loss in the frequency band range of 2-18GHz is less than-10 dB, and the maximum value of the embodiment 2 can reach-13.97 dB. Meanwhile, although the reflection loss of comparative example 1 is very excellent (-14.57 dB) compared to example 2, the addition of CCNT greatly reduces the mechanical properties of the vulcanizate, which is not in accordance with the object of the present invention. Therefore, the silicon rubber wave-absorbing composite material optimized by the formula and the process has excellent tensile property, tearing strength, lower hardness and excellent electromagnetic wave absorption performance.
In the example (comparative examples 2 to 5) without the addition of HMDS, as shown in Table 2, the wave-absorbing property is not influenced by the modification of the white carbon black, and only the mechanical property of the vulcanized rubber is influenced, so that the wave-absorbing capability is not tested. The results show that when no HMDS is added, the white carbon black is agglomerated, has stress concentration points and has powder extraction at the fracture surface.
TABLE 2 vulcanizate tensile Properties, tear Strength (Right Angle), hardness
Figure BDA0003226508690000202
Figure BDA0003226508690000211
Examples of addition of the modifier KH570 (comparative examples 6 to 9) are shown in Table 3. KH570 can be used for surface treatment of inorganic fillers such as white carbon black, talc, clay, mica, pottery clay and kaolin, so as to improve the binding power to inorganic materials, increase the water resistance and reduce the curing temperature. However, when KH570 is added as a modifier to the rubber composite, there is a limited increase in mechanical properties.
TABLE 3 vulcanizate tensile Properties, tear Strength (Right Angle), hardness
Figure BDA0003226508690000212
Examples of addition of the modifier KH151 (comparative examples 10 to 13) are shown in Table 4. With other silane coupling agents, KH151 is mainly used for the binding force, compatibility and adhesive force of inorganic powder materials to high molecular polymers. However, when the modifier is added to the rubber composite material, the mechanical property is increased to a limited extent.
TABLE 4 vulcanizate tensile Properties, tear Strength (Right Angle), hardness
Figure BDA0003226508690000213
Addition of non-ball milled Fe 3 O 4 The properties of the microsphere examples (comparative examples 14-16) are shown in Table 5. Fe of large particle size 3 O 4 Agglomeration of the microspheres also occurs and microwave absorption is poor due to the lack of excellent dispersion in the matrix rubber.
TABLE 5 vulcanizate tensile, tear Strength (Right Angle), hardness, and maximum vertical Reflection Loss (RL)
Figure BDA0003226508690000221
(2) Examples 1-3, comparative example 1 and pure vulcanized silicone rubber were subjected to an aging treatment. The aging conditions were: 200 ℃ for 24h in air atmosphere. The performance goals that are desired to be achieved are: the tensile strength is more than or equal to 2-5MPa, the elongation at break is more than or equal to 120-240 percent, and the hardness is 30-40 degrees.
And testing the tensile property and Shore A hardness of the aged vulcanized rubber at a tensile speed of 500mm/min by adopting Chinese national standards GB/T528-2009 and GB/T529-2008.
The results are shown in Table 6:
TABLE 6 tensile Properties and hardness of vulcanizates after Hot air aging treatment
Figure BDA0003226508690000222
As can be seen from the above table, after the hot air aging treatment, the tensile strength of examples 1 to 3 is maintained within 4.5 to 5.0MPa, the elongation at break is greater than 290%, the Shore A hardness is maintained within the range of 30 to 40 degrees, and the excellent aging resistance is achieved.
(3) Examples 1 to 3, comparative example 1 and pure vulcanized silicone rubber were subjected to a moist heat aging treatment, the moist heat test being carried out as specified in relation to GJB150.9A-2009 (temperature 60 ℃, relative humidity 95%) for a cycle of 24h for 6 cycles. The retention rate of the samples 1-3 is above 80%, no water drop is adsorbed on the surface, only free water drops are condensed on the surface, and the water drops disappear after the temperature is returned to room temperature.
The change in properties after humid heat ageing is shown in Table 7.
TABLE 7 tensile Properties and hardness of vulcanizates after Damp-Heat aging treatment
Figure BDA0003226508690000231
While specific embodiments of the invention have been described above, it will be appreciated by those skilled in the art that this is by way of example only, and that the scope of the invention is defined by the appended claims. Various changes and modifications to these embodiments may be made by those skilled in the art without departing from the spirit and scope of the invention, and these changes and modifications are within the scope of the invention.

Claims (13)

1. The raw material composition of the silicone rubber composite material is characterized by comprising the following components: silicon rubber, white carbon black and Fe 3 O 4 Graphene, a modifier, a lubricant, and a crosslinker; said Fe 3 O 4 Has a median particle diameter (D50) of 600 to 1000nm, the modifier being Hexamethyldisilazane (HMDS);
wherein, the silicon rubber, the white carbon black and the Fe 3 O 4 And the mass ratio of the graphene to the lubricant is 100: (30-50): (1-30): (0.5-2): (1-10), wherein the mass ratio of the modifier to the white carbon black is (15-25): 100, respectively;
the mass ratio of the cross-linking agent to other components is (1-5): 100, the other components refer to the sum of the components of the raw material composition except the cross-linking agent;
the silicone rubber is methyl vinyl silicone rubber;
the white carbon black is gas-phase white carbon black or precipitation white carbon black;
the graphene is a graphene nanosheet;
the lubricant is polydimethylsiloxane;
the cross-linking agent is 2,5-dimethyl-2,5-bis (t-butylperoxy) hexane.
2. The raw material composition of the silicone rubber composite material as claimed in claim 1, wherein the vinyl content in the silicone rubber is 0.1% to 0.2%.
3. A feedstock composition for a silicone rubber composite as defined in claim 1, wherein said feedstock composition satisfies one or more of the following conditions:
(1) The mass ratio of the white carbon black to the silicone rubber is (35-45): 100, respectively;
(2) Said Fe 3 O 4 And the mass ratio of the silicon rubber to the silicon rubber is (3-25): 100;
(3) The mass ratio of the graphene to the silicon rubber is (0.8-1.5): 100, respectively;
(4) The mass ratio of the lubricant to the silicone rubber is (2-6): 100;
(5) The mass ratio of the modifier to the white carbon black is (15-20): 100;
(6) The mass ratio of the cross-linking agent to other components is (1-3): 100.
4. the raw material composition of the silicone rubber composite material according to claim 1, wherein in the raw material composition, silicone rubber, white carbon black, and Fe 3 O 4 And the mass ratio of the graphene to the lubricant is 100: (35-45): (3-25): (0.8-1.5): (2-6), the mass ratio of the modifier to the white carbon black is (15-20): 100, the mass ratio of the cross-linking agent to other components is (1-3): 100.
5. a feedstock composition for a silicone rubber composite as defined in claim 1, wherein said feedstock composition satisfies one or more of the following conditions:
(1) The silicon rubber is methyl vinyl silicon rubber 110-2;
(2) The vinyl content in the silicone rubber is 0.19%;
(3) The white carbon black is fumed silica;
(4) Said Fe 3 O 4 Has a median particle diameter of 900nm;
(5) The graphene is a graphene nanosheet with a lamella size of 20-30 mu m and a thickness of 5-8 nm;
(6) The mass ratio of the white carbon black to the silicone rubber is 40:100, respectively;
(7) Said Fe 3 O 4 And the mass ratio of the silicon rubber is 5:100 or 20:100;
(8) The mass ratio of the graphene to the silicon rubber is 1;
(9) The mass ratio of the lubricant to the silicone rubber is 4;
(10) The mass ratio of the modifier to the white carbon black is 18:100, respectively;
(11) The mass ratio of the cross-linking agent to other components is 2;
(12) The raw material composition consists of the following components: silicon rubber, white carbon black and Fe 3 O 4 Graphene, a modifier, a lubricant, and a crosslinker.
6. The raw material composition for silicone rubber composite material according to claim 1, characterized in that the raw material composition satisfies one of the following conditions:
(1) The raw material composition comprises the following components in parts by mass:
Figure FDA0003899370070000021
(2) The raw material composition comprises the following components in parts by mass:
Figure FDA0003899370070000031
(3) The raw material composition comprises the following components in parts by mass:
Figure FDA0003899370070000032
7. a process for the preparation of a silicone rubber composite, characterized in that it is prepared using a starting composition according to any one of claims 1 to 6, said process comprising the steps of:
(1) Mixing the components except the cross-linking agent in the raw material composition to obtain a rubber compound;
(2) And vulcanizing the rubber compound and a cross-linking agent.
8. The method of preparing a silicone rubber composite material according to claim 7, wherein the method of preparation satisfies one or more of the following conditions:
(1) The mixing is carried out on an open mill;
(2) The mixing temperature is 60-100 ℃;
(3) The mixing comprises the following steps: adding a part of white carbon black, then adding silicon rubber, adding the rest of white carbon black for several times, adding the modifier after adding the white carbon black each time, mixing uniformly, and then adding Fe 3 O 4 And graphene, and finally adding a lubricant;
(4) The mixing method further comprises a standing step to remove bubbles and volatile substances after the mixing is finished, wherein the standing temperature is 60-80 ℃, and the standing time is 1.5-3h;
(5) The vulcanization is carried out by using a hot press;
(6) The vulcanization temperature is 160-190 ℃;
(7) The vulcanization time is 10-15min;
(8) The pressure of the vulcanization is 5-20MPa;
(9) And after the vulcanization is finished, the method also comprises a secondary vulcanization step, wherein the temperature of the secondary vulcanization is 160-220 ℃, and the time of the secondary vulcanization is 2-5h.
9. The method of preparing a silicone rubber composite material according to claim 8, wherein the method of preparation satisfies one or more of the following conditions:
(1) The mixing temperature is 60 ℃;
(2) The mixing comprises the following steps: adding a part of white carbon black, then adding silicon rubber, adding the rest white carbon black for 2-10 times, adding the modifier after adding the white carbon black each time, mixing uniformly, and then adding Fe 3 O 4 And graphene, and finally adding a lubricant;
(3) The mixing method further comprises a standing step to remove bubbles and volatile substances after the mixing is finished, wherein the standing temperature is 60 ℃, and the standing time is 2 hours;
(4) The temperature of the vulcanization is 180 ℃;
(5) The vulcanization time is 12min;
(6) The vulcanization pressure is prepressing at 5-12Mpa for 2-8min, and then pressurizing at 10-20Mpa for 2-10min; in order to fully remove residual gas in the vulcanized rubber, exhausting for 10-15 times after pre-pressing and starting pressurization for about 2min;
(7) And after the vulcanization is finished, the method also comprises a secondary vulcanization step, wherein the temperature of the secondary vulcanization is 200 ℃, and the time of the secondary vulcanization is 4h.
10. The method of preparing a silicone rubber composite material according to claim 9, wherein the method of preparation satisfies one or more of the following conditions:
(1) The mixing comprises the following steps: adding a part of white carbon black, then adding silicon rubber, adding the rest white carbon black for 7 times, adding the modifier after adding the white carbon black each time, mixing uniformly, and then adding Fe 3 O 4 And graphene, and finally adding a lubricant;
(2) The vulcanization pressure is prepressing at 5Mpa for 2min, and then pressurizing at 10Mpa for 10min; in order to fully remove residual gas in the vulcanized rubber, 10-15 times of air exhaust is carried out after pre-pressing and starting pressurization for about 2min.
11. A silicone rubber composite material prepared from the raw material composition as set forth in any one of claims 1 to 6.
12. The silicone rubber composite of claim 11; the silicone rubber composite is produced by the method for producing a silicone rubber composite as defined in any one of claims 7 to 10.
13. Use of the silicone rubber composite material according to claim 11 as an electromagnetic shielding material.
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