CN105820580A - High-strength silicone rubber electromagnetic shielding material and preparing method thereof - Google Patents
High-strength silicone rubber electromagnetic shielding material and preparing method thereof Download PDFInfo
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Abstract
The invention discloses a high-strength silicone rubber electromagnetic shielding material. The material comprises, by weight, 100-120 parts of hydroxyl terminated polydimethylsiloxane, 60-80 parts of fluorosilane modified halloysite nanotube, 5-12 parts of silicon dioxide powder with a nickel-plated surface, 10-15 parts of modified carbon nano tube, 16-20 parts of fumed silica, 2-5 parts of cross-linking agent and 0.1-0.5 part of catalyst. The invention further discloses a preparing method of the high-strength silicone rubber electromagnetic shielding material. The material is high in electromagnetic shielding property and excellent in mechanical property, has a certain hydrophobic property and is highly practical. Furthermore, the preparing method is simple, production cost is low, and safety and environment friendliness are high.
Description
Technical field:
The present invention relates to technical field of electromagnetic shielding, be specifically related to a kind of high-strength silicone rubber electromagnetic shielding material
Material.
Background technology:
Along with science and technology and the high speed development of electronics industry, increasing digitized, informationization and electronics electricity
Device equipment operationally a large amount of different wave lengths and the electromagnetic wave of frequency to space radiation, thus result in new ring
Environment pollution Electromagnetic Interference and radiofrequency interference.Cause electromagnetic wave become the sound pollution that continues, atmospheric pollution,
Another big public hazards after water pollution, solid waste pollution.Electromagnetic Interference and radiofrequency are disturbed and shields
One of effective measures covered, are the places easily revealing electromagnetic wave at the casing seam portion and hole of electronic device
Closed with screening conductive material.Silicone rubber is one of staple product in organosilicon polymer, has very
Excellent thermostability, tolerance to cold and electrical property, therefore, it can the base as good composite electromagnetic shield materials
Body material.
Electromagnetic shielding is generally divided into 3 classes, the respectively shielding of electrostatic screen, magnetic shielding and electromagnetic field of high frequency.
The general character of 3 kinds of shieldings is to prevent from the electromagnetic field in the external world from entering into certain to need in area to be protected, wherein electromagnetism
The reflection of ripple plays a major role in the shield.But existing silicone rubber electromagnetic shielding material mechanical property is poor,
And weatherability is bad, water proofing property is poor, has had a strong impact on its service life.
Summary of the invention:
It is an object of the invention to provide a kind of high-strength silicone rubber electromagnetic shielding material, its capability of electromagnetic shielding is good, power
Learn excellent performance, and there is certain hydrophobicity, good stability.
It is a further object to provide the preparation method of this high-strength silicone rubber electromagnetic shielding material.
For achieving the above object, the present invention is by the following technical solutions:
A kind of high-strength silicone rubber electromagnetic shielding material, in parts by weight, including following components:
Hydroxyl-terminated injecting two methyl siloxane 100-120 part,
Halloysite nanotubes 60-80 part that silicon fluoride is modified,
Silicon dioxide powder 5-12 part of plating nickel on surface,
Modified carbon nano-tube 10-15 part,
Fume colloidal silica 16-20 part,
Cross-linking agent 2-5 part,
Catalyst 0.1-0.5 part.
Preferred as technique scheme, a kind of high-strength silicone rubber electromagnetic shielding material, in parts by weight, bag
Include following components:
Hydroxyl-terminated injecting two methyl siloxane 115 parts,
The halloysite nanotubes 75 parts that silicon fluoride is modified,
The silicon dioxide powder of plating nickel on surface 10 parts,
Modified carbon nano-tube 12 parts,
Fume colloidal silica 18 parts,
Cross-linking agent 3.5 parts,
Catalyst 0.13 part.
Preferred as technique scheme, the molecular weight of described hydroxyl-terminated injecting two methyl siloxane is
10000-20000。
Preferred as technique scheme, the size of the silicon dioxide powder of described plating nickel on surface is
20-50nm。
Preferred as technique scheme, the preparation method of modified carbon nano-tube comprises the following steps: first will
CNT carries out carboxylated process, then filtration drying, and by carboxylated CNT, vinyl front three
TMOS joins in the ethanol water that concentration is 70%, stirs 5-10h, treat certainly under 70-100 DEG C of oil bath
After being so cooled to room temperature, filter, vacuum drying, obtain modified carbon nano-tube.
Preferred as technique scheme, the silicon fluoride in described silicon fluoride modification halloysite nanotubes is perfluor
Octyltri-ethoxysilane, 17 fluorine trimethoxy Ethoxysilanes, 17 fluorine decyl trimethoxy silanes, five
Any one in fluorophenyl dimethylchlorosilane and ten difluoro heptyl propyl trimethoxy silicanes.
Preferred as technique scheme, described catalyst is the Organometallic compounds of chloroplatinic acid, platiniferous or palladium
One in thing, organic metal chelate complex.
The preparation method of a kind of high-strength silicone rubber electromagnetic shielding material, comprises the following steps:
(1) in vacuum kneader, add hydroxyl-terminated injecting two methyl siloxane, add under 80-120 DEG C of vacuum
The halloysite nanotubes that fume colloidal silica, silicon fluoride are modified, stirring mixing 2-5h, it is transferred to after mix homogeneously
In two roller rubber mixing machines, and it is sequentially added into cross-linking agent, modified carbon nano-tube, the silicon dioxide powder of plating nickel on surface and urges
Agent, at 30-40 DEG C, mixing 10-20min, obtains elastomeric compound;
(2) mixing roll that step (1) prepares carries out one step cure successively to process and post vulcanization process, system
Obtain high-strength silicone rubber electromagnetic shielding material.
Preferred as technique scheme, in step (2), described one step cure temperature is 160-170 DEG C,
The one step cure time is 15-30min, and sulfide stress is 10-25MPa.
Preferred as technique scheme, in step (2), described post vulcanization includes two temperature rise periods
With a constant temperature stage, wherein first temperature rise period temperature rises to 150-165 DEG C from room temperature, and programming rate is
4 DEG C/min, second temperature rise period is to rise to 200-215 DEG C from 150-165 DEG C, and programming rate is 0.5 DEG C
/ min, the constant temperature stage is 200-215 DEG C, and constant temperature time is 4-6h.
The method have the advantages that
The present invention adds modified carbon nano-tube, gas-phase silica and silicon fluoride in silicone rubber electromagnetic shielding material
Modified halloysite nanotubes, three is the most collaborative so that system material not only there is good electromagnetic shielding
Performance, and excellent in mechanical performance, hydrophobic performance is good, thus substantially increases its serviceability;
Silicone rubber electromagnetic shielding material good stability prepared by the present invention, preparation technology is simple, and production cost is low,
And safety and environmental protection.
Detailed description of the invention:
In order to be better understood from the present invention, below by embodiment, the present invention is further described, and embodiment is only used
In explaining the present invention, the present invention will not be constituted any restriction.
Embodiment 1
A kind of high-strength silicone rubber electromagnetic shielding material, in parts by weight, including following components:
Hydroxyl-terminated injecting two methyl siloxane 100 parts,
The halloysite nanotubes 60 parts that silicon fluoride is modified,
The silicon dioxide powder of plating nickel on surface 5 parts, modified carbon nano-tube 10 parts,
Fume colloidal silica 16 parts, cross-linking agent 2 parts, catalyst 0.1 part.
Its preparation method comprises the following steps:
(1) preparation of modified carbon nano-tube:
First CNT is carried out carboxylated process, then filtration drying, and by carboxylated CNT,
Vinyltrimethoxy silane joins in the ethanol water that concentration is 70%, stirs 5h, treat under 70 DEG C of oil baths
After naturally cooling to room temperature, filter, vacuum drying, obtain modified carbon nano-tube;
(2) in vacuum kneader, add hydroxyl-terminated injecting two methyl siloxane, under 80 DEG C of vacuum, add gas phase
The halloysite nanotubes that method white carbon, silicon fluoride are modified, stirring mixing 2-5h, it is transferred to two rollers after mix homogeneously
In rubber mixing machine, and it is sequentially added into cross-linking agent, modified carbon nano-tube, the silicon dioxide powder of plating nickel on surface and catalyst,
At 30 DEG C, mixing 10min, obtains elastomeric compound;
(3) mixing roll that step (2) prepares carries out one step cure successively to process and post vulcanization process, system
Obtaining high-strength silicone rubber electromagnetic shielding material, wherein one step cure temperature is 160 DEG C, and the one step cure time is 15min,
Sulfide stress is 10MPa;Post vulcanization includes two temperature rise periods and a constant temperature stage, and wherein first rises
Thermophase temperature rises to 150 DEG C from room temperature, and programming rate is 4 DEG C/min, and second temperature rise period is from 150 DEG C
Rising to 200 DEG C, programming rate is 0.5 DEG C/min, and the constant temperature stage is 200 DEG C, and constant temperature time is 4h.
Embodiment 2
A kind of high-strength silicone rubber electromagnetic shielding material, in parts by weight, including following components:
Hydroxyl-terminated injecting two methyl siloxane 120 parts,
The halloysite nanotubes 80 parts that silicon fluoride is modified,
The silicon dioxide powder of plating nickel on surface 12 parts, modified carbon nano-tube 15 parts,
Fume colloidal silica 20 parts, cross-linking agent 5 parts, catalyst 0.5 part.
Its preparation method comprises the following steps:
(1) preparation of modified carbon nano-tube:
First CNT is carried out carboxylated process, then filtration drying, and by carboxylated CNT,
Vinyltrimethoxy silane joins in the ethanol water that concentration is 70%, stirs 10h under 100 DEG C of oil baths,
After room temperature, filter, vacuum drying, obtain modified carbon nano-tube;
(2) in vacuum kneader, add hydroxyl-terminated injecting two methyl siloxane, under 120 DEG C of vacuum, add gas phase
The halloysite nanotubes that method white carbon, silicon fluoride are modified, stirring mixing 5h, it is transferred to two roll milling after mix homogeneously
In glue machine, and it is sequentially added into cross-linking agent, modified carbon nano-tube, the silicon dioxide powder of plating nickel on surface and catalyst,
At 40 DEG C, mixing 20min, obtains elastomeric compound;
(3) mixing roll that step (2) prepares carries out one step cure successively to process and post vulcanization process, system
Obtaining high-strength silicone rubber electromagnetic shielding material, wherein one step cure temperature is 170 DEG C, and the one step cure time is 30min,
Sulfide stress is 25MPa;Post vulcanization includes two temperature rise periods and a constant temperature stage, and wherein first rises
Thermophase temperature rises to 165 DEG C from room temperature, and programming rate is 4 DEG C/min, and second temperature rise period is from 165 DEG C
Rising to 215 DEG C, programming rate is 0.5 DEG C/min, and the constant temperature stage is 215 DEG C, and constant temperature time is 6h.
Embodiment 3
A kind of high-strength silicone rubber electromagnetic shielding material, in parts by weight, including following components:
Hydroxyl-terminated injecting two methyl siloxane 105 parts,
The halloysite nanotubes 65 parts that silicon fluoride is modified,
The silicon dioxide powder of plating nickel on surface 7 parts, modified carbon nano-tube 11 parts,
Fume colloidal silica 17 parts, cross-linking agent 3 parts, catalyst 0.2 part.
Its preparation method comprises the following steps:
(1) preparation of modified carbon nano-tube:
First CNT is carried out carboxylated process, then filtration drying, and by carboxylated CNT,
Vinyltrimethoxy silane joins in the ethanol water that concentration is 70%, stirs 6h, treat under 75 DEG C of oil baths
After naturally cooling to room temperature, filter, vacuum drying, obtain modified carbon nano-tube;
(2) in vacuum kneader, add hydroxyl-terminated injecting two methyl siloxane, under 90 DEG C of vacuum, add gas phase
The halloysite nanotubes that method white carbon, silicon fluoride are modified, stirring mixing 3h, it is transferred to two roll milling after mix homogeneously
In glue machine, and it is sequentially added into cross-linking agent, modified carbon nano-tube, the silicon dioxide powder of plating nickel on surface and catalyst,
At 35 DEG C, mixing 12min, obtains elastomeric compound;
(3) mixing roll that step (2) prepares carries out one step cure successively to process and post vulcanization process, system
Obtaining high-strength silicone rubber electromagnetic shielding material, wherein one step cure temperature is 162 DEG C, and the one step cure time is 18min,
Sulfide stress is 15MPa;Post vulcanization includes two temperature rise periods and a constant temperature stage, and wherein first rises
Thermophase temperature rises to 155 DEG C from room temperature, and programming rate is 4 DEG C/min, and second temperature rise period is from 155 DEG C
Rising to 205 DEG C, programming rate is 0.5 DEG C/min, and the constant temperature stage is 205 DEG C, and constant temperature time is 4.5h.
Embodiment 4
A kind of high-strength silicone rubber electromagnetic shielding material, in parts by weight, including following components:
Hydroxyl-terminated injecting two methyl siloxane 110 parts,
The halloysite nanotubes 70 parts that silicon fluoride is modified,
The silicon dioxide powder of plating nickel on surface 9 parts, modified carbon nano-tube 12 parts,
Fume colloidal silica 18 parts, cross-linking agent 3.5 parts, catalyst 0.3 part.
Its preparation method comprises the following steps:
(1) preparation of modified carbon nano-tube:
First CNT is carried out carboxylated process, then filtration drying, and by carboxylated CNT,
Vinyltrimethoxy silane joins in the ethanol water that concentration is 70%, stirs 7h, treat under 80 DEG C of oil baths
After naturally cooling to room temperature, filter, vacuum drying, obtain modified carbon nano-tube;
(2) in vacuum kneader, add hydroxyl-terminated injecting two methyl siloxane, under 100 DEG C of vacuum, add gas phase
The halloysite nanotubes that method white carbon, silicon fluoride are modified, stirring mixing 3.5h, it is transferred to two rollers after mix homogeneously
In rubber mixing machine, and it is sequentially added into cross-linking agent, modified carbon nano-tube, the silicon dioxide powder of plating nickel on surface and catalyst,
At 30 DEG C, mixing 14min, obtains elastomeric compound;
(3) mixing roll that step (2) prepares carries out one step cure successively to process and post vulcanization process, system
Obtaining high-strength silicone rubber electromagnetic shielding material, wherein one step cure temperature is 164 DEG C, and the one step cure time is 20min,
Sulfide stress is 20MPa;Post vulcanization includes two temperature rise periods and a constant temperature stage, and wherein first rises
Thermophase temperature rises to 160 DEG C from room temperature, and programming rate is 4 DEG C/min, and second temperature rise period is from 160 DEG C
Rising to 210 DEG C, programming rate is 0.5 DEG C/min, and the constant temperature stage is 210 DEG C, and constant temperature time is 5h.
Embodiment 5
A kind of high-strength silicone rubber electromagnetic shielding material, in parts by weight, including following components:
Hydroxyl-terminated injecting two methyl siloxane 115 parts,
The halloysite nanotubes 75 parts that silicon fluoride is modified,
The silicon dioxide powder of plating nickel on surface 10 parts, modified carbon nano-tube 13 parts,
Fume colloidal silica 19 parts, cross-linking agent 4 parts, catalyst 0.4 part.
Its preparation method comprises the following steps:
(1) preparation of modified carbon nano-tube:
First CNT is carried out carboxylated process, then filtration drying, and by carboxylated CNT,
Vinyltrimethoxy silane joins in the ethanol water that concentration is 70%, stirs 8h, treat under 85 DEG C of oil baths
After naturally cooling to room temperature, filter, vacuum drying, obtain modified carbon nano-tube;
(2) in vacuum kneader, add hydroxyl-terminated injecting two methyl siloxane, under 110 DEG C of vacuum, add gas phase
The halloysite nanotubes that method white carbon, silicon fluoride are modified, stirring mixing 4h, it is transferred to two roll milling after mix homogeneously
In glue machine, and it is sequentially added into cross-linking agent, modified carbon nano-tube, the silicon dioxide powder of plating nickel on surface and catalyst,
At 35 DEG C, mixing 16min, obtains elastomeric compound;
(3) mixing roll that step (2) prepares carries out one step cure successively to process and post vulcanization process, system
Obtaining high-strength silicone rubber electromagnetic shielding material, wherein one step cure temperature is 166 DEG C, and the one step cure time is 25min,
Sulfide stress is 20MPa;Post vulcanization includes two temperature rise periods and a constant temperature stage, and wherein first rises
Thermophase temperature rises to 165 DEG C from room temperature, and programming rate is 4 DEG C/min, and second temperature rise period is from 165 DEG C
Rising to 210 DEG C, programming rate is 0.5 DEG C/min, and the constant temperature stage is 210 DEG C, and constant temperature time is 5.5h.
Embodiment 6
A kind of high-strength silicone rubber electromagnetic shielding material, in parts by weight, including following components:
Hydroxyl-terminated injecting two methyl siloxane 118 parts,
The halloysite nanotubes 80 parts that silicon fluoride is modified,
The silicon dioxide powder of plating nickel on surface 11 parts, modified carbon nano-tube 14 parts,
Fume colloidal silica 19.5 parts, cross-linking agent 4.5 parts, catalyst 0.45 part.
Its preparation method comprises the following steps:
(1) preparation of modified carbon nano-tube:
First CNT is carried out carboxylated process, then filtration drying, and by carboxylated CNT,
Vinyltrimethoxy silane joins in the ethanol water that concentration is 70%, stirs 9h, treat under 95 DEG C of oil baths
After naturally cooling to room temperature, filter, vacuum drying, obtain modified carbon nano-tube;
(2) in vacuum kneader, add hydroxyl-terminated injecting two methyl siloxane, under 115 DEG C of vacuum, add gas phase
The halloysite nanotubes that method white carbon, silicon fluoride are modified, stirring mixing 4.5h, it is transferred to two rollers after mix homogeneously
In rubber mixing machine, and it is sequentially added into cross-linking agent, modified carbon nano-tube, the silicon dioxide powder of plating nickel on surface and catalyst,
At 40 DEG C, mixing 18min, obtains elastomeric compound;
(3) mixing roll that step (2) prepares carries out one step cure successively to process and post vulcanization process, system
Obtaining high-strength silicone rubber electromagnetic shielding material, wherein one step cure temperature is 170 DEG C, and the one step cure time is 28min,
Sulfide stress is 25MPa;Post vulcanization includes two temperature rise periods and a constant temperature stage, and wherein first rises
Thermophase temperature rises to 160 DEG C from room temperature, and programming rate is 4 DEG C/min, and second temperature rise period is from 160 DEG C
Rising to 215 DEG C, programming rate is 0.5 DEG C/min, and the constant temperature stage is 215 DEG C, and constant temperature time is 6h.
Claims (10)
1. a high-strength silicone rubber electromagnetic shielding material, it is characterised in that in parts by weight, including following components:
Hydroxyl-terminated injecting two methyl siloxane 100-120 part,
Halloysite nanotubes 60-80 part that silicon fluoride is modified,
Silicon dioxide powder 5-12 part of plating nickel on surface,
Modified carbon nano-tube 10-15 part,
Fume colloidal silica 16-20 part,
Cross-linking agent 2-5 part,
Catalyst 0.1-0.5 part.
A kind of high-strength silicone rubber electromagnetic shielding material the most as claimed in claim 1, it is characterised in that in parts by weight,
Including following components:
Hydroxyl-terminated injecting two methyl siloxane 115 parts,
The halloysite nanotubes 75 parts that silicon fluoride is modified,
The silicon dioxide powder of plating nickel on surface 10 parts,
Modified carbon nano-tube 12 parts,
Fume colloidal silica 18 parts,
Cross-linking agent 3.5 parts,
Catalyst 0.13 part.
A kind of high-strength silicone rubber electromagnetic shielding material the most as claimed in claim 1, it is characterised in that described terminal hydroxy group
The molecular weight of polydimethylsiloxane is 10000-20000.
A kind of high-strength silicone rubber electromagnetic shielding material the most as claimed in claim 1, it is characterised in that described plated surface
The size of the silicon dioxide powder of nickel is 20-50nm.
A kind of high-strength silicone rubber electromagnetic shielding material the most as claimed in claim 1, it is characterised in that modified carbon nano tube
The preparation method of pipe comprises the following steps: first CNT carries out carboxylated process, then filtration drying, and will
Carboxylated CNT, vinyltrimethoxy silane join in the ethanol water that concentration is 70%, 70-100 DEG C
Stir 5-10h under oil bath, after room temperature, filter, vacuum drying, obtain modified carbon nano-tube.
A kind of high-strength silicone rubber electromagnetic shielding material the most as claimed in claim 1, it is characterised in that described silicon fluoride
Silicon fluoride in modified halloysite nanotubes be perfluoro capryl triethoxysilane, 17 fluorine trimethoxy Ethoxysilanes,
In 17 fluorine decyl trimethoxy silanes, pentafluorophenyl group dimethylchlorosilane and ten difluoro heptyl propyl trimethoxy silicanes
Any one.
A kind of high-strength silicone rubber electromagnetic shielding material the most as claimed in claim 1, it is characterised in that described catalyst
For the one in the organo-metallic compound of chloroplatinic acid, platiniferous or palladium, organic metal chelate complex.
8. the preparation method of a kind of high-strength silicone rubber electromagnetic shielding material as described in claim 1 to 7 is arbitrary, it is special
Levy and be, comprise the following steps:
(1) in vacuum kneader, add hydroxyl-terminated injecting two methyl siloxane, under 80-120 DEG C of vacuum, add vapor phase method
The halloysite nanotubes that white carbon, silicon fluoride are modified, stirring mixing 2-5h, it is transferred to two roller rubber mixing machines after mix homogeneously
In, and it is sequentially added into cross-linking agent, modified carbon nano-tube, the silicon dioxide powder of plating nickel on surface and catalyst, at 30-40 DEG C
Mixing 10-20min, obtains elastomeric compound;
(2) mixing roll that step (1) prepares carries out one step cure successively to process and post vulcanization process, prepare height
Strong silicone rubber electromagnetic shielding material.
The preparation method of a kind of high-strength silicone rubber electromagnetic shielding material the most as claimed in claim 8, it is characterised in that
In step (2), described one step cure temperature is 160-170 DEG C, and the one step cure time is 15-30min, sulfide stress
For 10-25MPa.
The preparation method of a kind of high-strength silicone rubber electromagnetic shielding material the most as claimed in claim 8, it is characterised in that
In step (2), described post vulcanization includes two temperature rise periods and a constant temperature stage, wherein first temperature rise period
Temperature rises to 150-165 DEG C from room temperature, and programming rate is 4 DEG C/min, and second temperature rise period is to rise from 150-165 DEG C
To 200-215 DEG C, programming rate is 0.5 DEG C/min, and the constant temperature stage is 200-215 DEG C, and constant temperature time is 4-6h.
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CN109334190A (en) * | 2018-09-14 | 2019-02-15 | 无锡新宏泰电器科技股份有限公司 | A kind of electromagnetic masking sheet molding compound and preparation method thereof |
CN110257022A (en) * | 2019-07-18 | 2019-09-20 | 深圳前海量子翼纳米碳科技有限公司 | A kind of electromagnetic shielding thermal conductive silicon rubber mat of insulation and preparation method thereof |
CN113980475A (en) * | 2021-10-08 | 2022-01-28 | 西北橡胶塑料研究设计院有限公司 | Low-density wide-frequency-band high-shielding-efficiency oil-resistant fluorosilicone rubber material and preparation method thereof |
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WO2024081360A1 (en) * | 2022-10-13 | 2024-04-18 | Laird Technologies, Inc. | Decreasing migration of materials from thermal management and/or electromagnetic interference (emi) mitigation materials |
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