CN109082123B - Graphene modified electromagnetic shielding silicon rubber material and preparation method thereof - Google Patents
Graphene modified electromagnetic shielding silicon rubber material and preparation method thereof Download PDFInfo
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- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
Abstract
The invention provides a graphene modified electromagnetic shielding silicone rubber material and a preparation method thereof, wherein the material at least comprises the following components in parts by weight: 100 parts of silicon rubber; 5-50 parts of graphene-silicon rubber; 0.2-1.0 part of a crosslinking agent; 10-150 parts of a metal conductive material; and 5-50 parts of an auxiliary agent. The method comprises at least the following steps: graphene, octamethylcyclotetrasiloxane (D4) and tetramethyltetravinylcyclotetrasiloxane (V4) are uniformly mixed and reacted under an anionic catalyst to obtain graphene-silicon rubber, and the graphene-silicon rubber and other components are mixed together according to a proportion. The material keeps the mechanical property equivalent to that of the prior art, the shielding effectiveness can reach 80dB at 300-1000MHz, and the density can be as low as 1.80g/cm3。
Description
Technical Field
The invention relates to an electromagnetic shielding rubber material, belongs to the field of electromagnetic shielding materials, and particularly relates to a graphene modified electromagnetic shielding silicon rubber material.
Background
In order to effectively inhibit electromagnetic interference and electromagnetic pollution, designing and preparing efficient electromagnetic shielding materials has become an urgent problem to be solved. At present, shielding conductive materials in the market are mainly metal, but the defects of the shielding conductive materials are that the mass is large, the price is high, and the shielding conductive materials are not easy to machine and form. With the development of the material industry, conductive rubber materials for shielding electromagnetic radiation are continuously developed and applied, and are gradually replacing pure metal shielding materials. The graphene filler is utilized, the dispersion and conduction mechanism of the graphene filler in rubber is researched, the requirements of small and light precision electronic devices can be met, the comprehensive performance of the electromagnetic shielding rubber is improved, and the development requirements of thinness, lightness, width and strength of the electromagnetic shielding rubber are met. However, graphene has substantially no groups on the surface, so that it is difficult to achieve uniform dispersion in a rubber matrix, and the density of graphene is high due to the need of adding a metal material in the prior art.
Disclosure of Invention
In view of the above-mentioned drawbacks of the prior art, an object of the present invention is to provide a graphene-modified electromagnetic shielding silicone rubber material and a preparation method thereof. The problem that the material density is high due to the fact that the using amount of metal fillers in the electromagnetic shielding rubber is high in the prior art is solved. Another problem to be solved by the present invention is: graphene is the most conductive material, and it is difficult to form a uniform and stable distribution with a rubber matrix because no other groups are present on the surface.
In order to achieve the above objects and other related objects, the present invention provides a graphene modified electromagnetic shielding silicone rubber material, which at least comprises the following components in parts by weight:
the graphene-silicon rubber is a composite formed by uniformly dispersing graphene in silicon rubber.
Preferably, the graphene modified electromagnetic shielding silicone rubber material at least further comprises the following components in parts by weight:
0.1-100 parts of a non-metallic conductive material; preferably 1-80 parts; more preferably 10 to 50 parts.
Preferably, the graphene modified electromagnetic shielding silicon rubber material comprises the following components in parts by weight:
preferably, the graphene modified electromagnetic shielding silicon rubber material comprises the following components in parts by weight:
preferably, the graphene modified electromagnetic shielding silicon rubber material comprises the following components in parts by weight:
further, the molecular weight of the silicon rubber is 35 ten thousand-150; preferably 50 to 100 ten thousand.
Further, the crosslinking agent is selected from any one or more of 2, 5-dimethyl-2, 5-di-tert-butyl hexane peroxide (DBPMH), di-tert-butyl peroxide (DTBP) and dicumyl peroxide (DCP).
Further, the metal conductive material is selected from one or more of silver powder, silver-plated copper powder and silver-plated aluminum powder.
Further, the non-metal conductive material is selected from any one or more of silver-plated glass beads, nickel-plated graphite, conductive carbon black and carbon nanotubes.
Further, the auxiliary agent is selected from any one or more of fillers, heat-resistant agents, release agents and structure control agents.
Further, the filler is selected from one or more of precipitated silica, diatomite and glass powder.
Further, the heat-resistant agent is selected from one or more of iron oxide, cerium oxide and zinc oxide.
Further, the release agent is one or two selected from stearic acid and zinc stearate.
Further, the structure control agent is selected from one or two of hydroxyl silicone oil and diphenyl silanediol.
In order to solve the above problems, another aspect of the present invention provides a preparation method of the graphene modified electromagnetic shielding silicon rubber material, where the method at least includes the following steps:
graphene, octamethylcyclotetrasiloxane (D4) and tetramethyltetravinylcyclotetrasiloxane (V4) are uniformly mixed and reacted under an anionic catalyst to obtain graphene-silicon rubber, and the graphene-silicon rubber and other components are mixed together according to a proportion.
Further, the anion catalyst is one or two of tetramethylammonium hydroxide silicon alkoxide or tetramethylammonium hydroxide.
Specifically, the method comprises the following steps:
(1) putting the octamethylcyclotetrasiloxane (D4) and tetramethyltetravinylcyclotetrasiloxane (V4) which are dried in vacuum into a reaction kettle in a protective atmosphere, adding an anion catalyst, adding graphene, and uniformly mixing to obtain the graphene-
Silicon rubber, and sealing;
(2) adding the components into an internal mixer according to a certain proportion, and blending to obtain a rubber compound;
(3) mixing the mixed glue and vulcanizing agent on an open mill, blending and vulcanizing.
Preferably, the step (1) is specifically: adding a catalyst, heating to 60-80 ℃, adding graphene, mixing at the speed of 800 plus or minus 2000rpm, keeping for 20-40 min, heating to 100 +/-10 ℃ for 1-3 h, heating to 150 +/-10 ℃ for 20-40 min, vacuumizing (50mmHg), heating to 180 +/-10 ℃ and keeping for 20-40 min.
Further, the mass ratio of octamethylcyclotetrasiloxane (D4) to tetramethyltetravinylcyclotetrasiloxane (V4) is 600: 1-700: 1.
Further, the mass ratio of the graphene to the octamethylcyclotetrasiloxane is 1: 10-1: 5.
Further, the mass ratio of the anionic catalyst to the octamethylcyclotetrasiloxane is 1: 10000.
Further, the anion catalyst is one or more of tetramethylammonium hydroxide silicon alkoxide and tetramethylammonium hydroxide.
Further, the protective gas is nitrogen or other inert gases.
Preferably, the mixing time of the internal mixer in the step (2) is 20-60 minutes.
Further, vacuumizing and cooling simultaneously during banburying in the step (2).
Further, the temperature of the sulfuration in the step (3) is 160-170 ℃, and the time is 5-10 minutes.
As described above, the graphene modified electromagnetic shielding silicone rubber material and the preparation method thereof of the present invention have the following beneficial effects:
the mechanical performance is kept equal to that of the prior art, the shielding effectiveness can reach 80dB at 300-1000MHz, and the density can be as low as 1.80g/cm3。
Detailed Description
The embodiments of the present invention are described below with reference to specific embodiments, and other advantages and effects of the present invention will be easily understood by those skilled in the art from the disclosure of the present specification. The invention is capable of other and different embodiments and of being practiced or of being carried out in various ways, and its several details are capable of modification in various respects, all without departing from the spirit and scope of the present invention. It is to be understood that the processing equipment or apparatus not specifically identified in the following examples is conventional in the art. Furthermore, it is to be understood that one or more method steps mentioned in the present invention does not exclude that other method steps may also be present before or after the combined steps or that other method steps may also be inserted between these explicitly mentioned steps, unless otherwise indicated; it is also to be understood that a combined connection between one or more devices/apparatus as referred to in the present application does not exclude that further devices/apparatus may be present before or after the combined device/apparatus or that further devices/apparatus may be interposed between two devices/apparatus explicitly referred to, unless otherwise indicated. Moreover, unless otherwise indicated, the numbering of the various method steps is merely a convenient tool for identifying the various method steps, and is not intended to limit the order in which the method steps are arranged or the scope of the invention in which the invention may be practiced, and changes or modifications in the relative relationship may be made without substantially changing the technical content.
Example 1
The raw materials are selected and matched according to the following weight portions:
firstly weighing vacuum-dried octamethylcyclotetrasiloxane (D4) and tetramethyltetravinylcyclotetrasiloxane (V4) (the mass ratio is 600:1) and placing the octamethylcyclotetrasiloxane and the tetramethyltetravinylcyclotetrasiloxane (V4) into a reaction kettle in a nitrogen atmosphere, adding 1% tetramethylammonium hydroxide silicon alkoxide (the mass ratio of the tetramethylammonium hydroxide silicon alkoxide to D4 is 1:100), heating to 60 ℃, adding graphene (the mass ratio of the graphene to D4 is 1:10), stirring at 1500rpm, keeping the stirring speed for 30min, heating to 100 ℃, keeping the temperature for 1 hour, and finally heating to 150 ℃ and keeping the temperature for 20 min. Then, vacuum was applied (50mmHg), the temperature was raised to 180 ℃ and the temperature was maintained for 20 min.
Putting the silicon rubber, the graphene master batch and other raw materials (except DBPMH) into an internal mixer according to a ratio, mixing for 40min, vacuumizing during internal mixing, and cooling at the same time to obtain an electromagnetic shielding silicon rubber compound; mixing the mixed glue and DBPMH on an open mill according to the proportion, mixing and blending, sizing and vulcanizing into a product on a flat vulcanizing machine by using a mould, wherein the vulcanizing conditions are as follows: 170 ℃ for 5 min.
And (3) detection of a product:
the performance of the product is detected by referring to a GJB 6190-:
table 1 example 1 results of performance testing
| Item | Unit of | Results |
| Tensile strength | MPa | 2.8 |
| Elongation at break | ％ | 180 |
| Density (23 ℃ C.) | g/cm3 | 4.1 |
| Shielding effectiveness (300-1000MHz) | dB | 92 |
Example 2
The raw materials are selected and matched according to the following weight portions:
firstly weighing vacuum-dried octamethylcyclotetrasiloxane (D4) and tetramethyltetravinylcyclotetrasiloxane (V4) (the mass ratio is 700:1) into a reaction kettle in a nitrogen atmosphere, adding 1% tetramethylammonium hydroxide (the mass ratio of the tetramethylammonium hydroxide to D4 is 1:100), heating to 70 ℃, adding graphene (the mass ratio of the graphene to D4 is 1:5), stirring at 2000rpm, keeping for 20min, heating to 110 ℃, keeping for 2 h, and finally heating to 160 ℃ and keeping for 40 min. Then, vacuum was applied (50mmHg), the temperature was raised to 170 ℃ and the temperature was maintained for 30 min.
Putting the silicon rubber, the graphene master batch and other raw materials (except DBPMH and DTBP) into an internal mixer according to the proportion, mixing for 40min, vacuumizing during internal mixing, and cooling at the same time to obtain an electromagnetic shielding silicon rubber compound; mixing the mixing rubber and DTBP, DBPMH on an open mill according to the proportion, mixing and blending, sizing and vulcanizing into a product on a flat vulcanizing machine by using a mould, wherein the vulcanizing conditions are as follows: 165 ℃ for 8 min.
And (3) detection of a product:
the performance of the product is detected by referring to a GJB 6190-:
table 2 example 2 results of performance testing
| Item | Unit of | Results |
| Tensile strength | MPa | 4.8 |
| Elongation at break | ％ | 300 |
| Density (23 ℃ C.) | g/cm3 | 3.2 |
| Shielding effectiveness (300-1000MHz) | dB | 89 |
Example 3
The raw materials are selected and matched according to the following weight portions:
firstly weighing vacuum-dried octamethylcyclotetrasiloxane (D4) and tetramethyltetravinylcyclotetrasiloxane (V4) (the mass ratio is 660:1) and placing the octamethylcyclotetrasiloxane and the tetramethyltetravinylcyclotetrasiloxane (V4) into a reaction kettle in a nitrogen atmosphere, adding 1% tetramethylammonium hydroxide (the mass ratio of the tetramethylammonium hydroxide to D4 is 1:100), heating to 80 ℃, adding graphene (the mass ratio of the graphene to D4 is 1.2:10), stirring at 2000rpm for 40min, heating to 90 ℃ for 4 hours, and finally heating to 150 ℃ for 30 min. Then, vacuum was applied (50mmHg), the temperature was raised to 190 ℃ and the temperature was maintained for 20 min.
Putting the silicon rubber, the graphene master batch and other raw materials (except DBPMH and DCP) into an internal mixer according to the proportion, mixing for 50min, vacuumizing during internal mixing, and cooling at the same time to obtain an electromagnetic shielding silicon rubber compound; mixing the mixing rubber, the DCP and the DBPMH on an open mill according to the proportion, carrying out open mixing and blending on the mixing rubber and the DCP and the DBPMH, and shaping and vulcanizing the mixture on a flat vulcanizing machine by using a mould to obtain a product, wherein the vulcanizing conditions are as follows: 160 ℃ for 10 min.
And (3) detection of a product:
the performance of the product is detected by referring to a GJB 6190-:
table 3 example 3 results of performance testing
| Item | Unit of | Results |
| Tensile strength | MPa | 3.7 |
| Elongation at break | ％ | 350 |
| Density (23 ℃ C.) | g/cm3 | 3.0 |
| Shielding effectiveness (300-1000MHz) | dB | 90 |
Example 4
The raw materials are selected and matched according to the following weight portions:
firstly weighing vacuum-dried octamethylcyclotetrasiloxane (D4) and tetramethyltetravinylcyclotetrasiloxane (V4) (the mass ratio is 660:1) into a reaction kettle in a nitrogen atmosphere, adding 1% tetramethylammonium hydroxide (the mass ratio of the tetramethylammonium hydroxide to D4 is 1:100), heating to 70 ℃, adding graphene (the mass ratio of the graphene to D4 is 1.2:10), stirring at the speed of 800rpm, keeping for 30min, heating to 100 ℃, keeping for 3 h, and finally heating to 150 ℃ and keeping for 30 min. Then, vacuum was applied (50mmHg), the temperature was raised to 180 ℃ and the temperature was maintained for 30 min.
Putting the silicon rubber, the graphene master batch and other raw materials (except DBPMH) into an internal mixer according to the proportion, mixing for 60min, vacuumizing during internal mixing, and cooling at the same time to obtain an electromagnetic shielding silicon rubber compound; mixing the mixed glue and DBPMH on an open mill according to the proportion, mixing and blending, sizing and vulcanizing into a product on a flat vulcanizing machine by using a mould, wherein the vulcanizing conditions are as follows: 170 ℃ for 5 min.
And (3) detection of a product:
the performance of the product is detected by referring to a GJB 6190-:
table 4 example 4 results of performance testing
| Item | Unit of | Results |
| Tensile strength | MPa | 1.6 |
| Elongation at break | ％ | 380 |
| Density (23 ℃ C.) | g/cm3 | 2.3 |
| Shielding effectiveness (300-1000MHz) | dB | 90 |
Example 5
The raw materials are selected and matched according to the following weight portions:
firstly weighing vacuum-dried octamethylcyclotetrasiloxane (D4) and tetramethyltetravinylcyclotetrasiloxane (V4) (the mass ratio is 660:1) into a reaction kettle in a nitrogen atmosphere, adding 1% tetramethylammonium hydroxide (the mass ratio of the tetramethylammonium hydroxide to D4 is 1:100), heating to 70 ℃, adding graphene (the mass ratio of the graphene to D4 is 1:10), stirring at 1200rpm, keeping for 30min, heating to 100 ℃, keeping for 3 h, and finally heating to 150 ℃ and keeping for 30 min. Then, vacuum was applied (50mmHg), the temperature was raised to 180 ℃ and the temperature was maintained for 30 min.
Putting the silicon rubber, the graphene master batch and other raw materials (except DBPMH) into an internal mixer according to the proportion, mixing for 60min, vacuumizing during internal mixing, and cooling at the same time to obtain an electromagnetic shielding silicon rubber compound; mixing the mixed glue and DBPMH on an open mill according to the proportion, mixing and blending, sizing and vulcanizing into a product on a flat vulcanizing machine by using a mould, wherein the vulcanizing conditions are as follows: 165 ℃ for 10 min.
And (3) detection of a product:
the performance of the product is detected by referring to a GJB 6190-:
table 5 example 5 results of performance testing
| Item | Unit of | Results |
| Tensile strength | MPa | 5.0 |
| Elongation at break | ％ | 400 |
| Density (23 ℃ C.) | g/cm3 | 1.8 |
| Shielding effectiveness (300-1000MHz) | dB | 82 |
The above examples are intended to illustrate the disclosed embodiments of the invention and are not to be construed as limiting the invention. In addition, various modifications of the methods and compositions set forth herein, as well as variations of the methods and compositions of the present invention, will be apparent to those skilled in the art without departing from the scope and spirit of the invention. While the invention has been specifically described in connection with various specific preferred embodiments thereof, it should be understood that the invention should not be unduly limited to such specific embodiments. Indeed, various modifications of the above-described embodiments which are obvious to those skilled in the art to which the invention pertains are intended to be covered by the scope of the present invention.
Claims (9)
1. The graphene modified electromagnetic shielding silicon rubber material is characterized by at least comprising the following raw materials in parts by weight:
the graphene-silicon rubber is a complex formed by uniformly dispersing graphene in silicon rubber; the preparation method comprises the following steps: putting the vacuum-dried octamethylcyclotetrasiloxane and tetramethyltetravinylcyclotetrasiloxane into a reaction kettle under a protective atmosphere, adding an anion catalyst, adding graphene, uniformly mixing to obtain graphene-silicon rubber, and sealing;
the non-metal conductive material is selected from any one or more of silver-plated glass beads, nickel-plated graphite, conductive carbon black and carbon nanotubes;
the auxiliary agent is selected from any one or more of filler, heat-resistant agent, release agent and structure control agent.
2. The graphene-modified electromagnetic shielding silicone rubber material of claim 1, wherein: the molecular weight of the silicone rubber is 50-100 ten thousand.
3. The graphene-modified electromagnetic shielding silicone rubber material of claim 1, wherein: the cross-linking agent is selected from any one or more of 2, 5-dimethyl-2, 5-di-tert-butyl hexane peroxide, di-tert-butyl peroxide and dicumyl peroxide.
4. The graphene-modified electromagnetic shielding silicone rubber material of claim 1, wherein: the metal conductive material is selected from one or more of silver powder, silver-plated copper powder and silver-plated aluminum powder.
5. The graphene-modified electromagnetic shielding silicone rubber material of claim 1, wherein: the graphene modified electromagnetic shielding silicone rubber material further comprises any one or more of the following technical characteristics:
(1) the filler is selected from one or more of precipitated silica, diatomite and glass powder;
(2) the heat-resistant agent is selected from one or more of ferric oxide, cerium oxide and zinc oxide;
(3) the release agent is selected from one or two of stearic acid and zinc stearate;
(4) the structure control agent is selected from one or two of hydroxyl silicone oil and diphenyl silanediol.
6. The preparation method of the graphene modified electromagnetic shielding silicone rubber material according to any one of claims 1 to 5, the method at least comprising the following steps:
graphene, octamethylcyclotetrasiloxane and tetramethyltetravinylcyclotetrasiloxane are mixed, and the mass ratio of the graphene to the octamethylcyclotetrasiloxane is 1: 10-1: 5; uniformly mixing and reacting under the presence of an anionic catalyst to obtain graphene-silicon rubber, and then mixing with other components in proportion.
7. The preparation method according to claim 6, wherein the preparation method specifically comprises:
(1) putting the vacuum-dried octamethylcyclotetrasiloxane and tetramethyltetravinylcyclotetrasiloxane into a reaction kettle under a protective atmosphere, adding an anion catalyst, adding graphene, uniformly mixing to obtain graphene-silicon rubber, and sealing;
(2) adding the components into an internal mixer according to a certain proportion, and blending to obtain a rubber compound;
(3) mixing the mixed glue and vulcanizing agent on an open mill, blending and vulcanizing.
8. The method of claim 7, wherein: the step (1) is specifically as follows: adding a catalyst, heating to 60-80 ℃, adding graphene, mixing at the speed of 800 plus or minus 2000rpm, keeping for 20-40 min, heating to 100 +/-10 ℃ for 1-3 h, heating to 150 +/-10 ℃ for 20-40 min, vacuumizing, heating to 180 +/-10 ℃ and keeping for 20-40 min.
9. The method of claim 7, wherein: the preparation method also comprises any one or more of the following technical characteristics:
1) the mass ratio of the octamethylcyclotetrasiloxane to the tetramethyltetravinylcyclotetrasiloxane is 600: 1-700: 1;
2) the mass ratio of the anionic catalyst to the octamethylcyclotetrasiloxane is 1: 10000;
3) the mixing time of the internal mixer in the step (2) is 20-60 minutes;
4) vacuumizing and cooling simultaneously during banburying in the step (2);
5) the temperature of the sulfuration in the step (3) is 160-170 ℃, and the time is 5-10 minutes.
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| CN110819117A (en) * | 2019-12-12 | 2020-02-21 | 哈尔滨工业大学 | Preparation method of silicone resin-graphene composite material |
| CN112322041A (en) * | 2020-11-11 | 2021-02-05 | 矽时代材料科技股份有限公司 | Electromagnetic shielding rubber and preparation method and application thereof |
| CN113956838A (en) * | 2021-11-02 | 2022-01-21 | 中国科学院长春应用化学研究所 | Radiation modified electromagnetic shielding silicone rubber self-adhesive tape and preparation method thereof |
| CN113999648A (en) * | 2021-12-20 | 2022-02-01 | 南通强生光电科技有限公司 | Graphene bottom sealing adhesive and preparation method thereof |
| CN114231041B (en) * | 2021-12-31 | 2023-05-02 | 上海电缆研究所有限公司 | B1-level flame-retardant ceramic low-smoke silicone rubber cable material and preparation method thereof |
| CN115340768A (en) * | 2022-09-30 | 2022-11-15 | 宁波恒浩广新型电子材料有限公司 | Preparation process and application of stainless steel-based electromagnetic shielding material |
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