CN103496228B - A kind of electromagnetic shielding structural conductive silicone rubber and preparation - Google Patents

Abstract

A kind of electromagnetic shielding structural conductive silicone rubber and preparation, belong to conductive polymer composite technical field.Use the double-deck or conductive silicon rubber composite of multiple structure, and it is coated with one layer of base glue as insulation adhesion coating, conductive silicon rubber composite: conductive powder, the silicone rubber matrix containing vinyldimethicone, acetylenic alcohol inhibitor, platinum catalyst, cross-linking agent at interlayer.The structural conductive silicone rubber that the present invention prepares, while ensureing General Mechanics performance requirement, can be effectively improved the shield effectiveness in the range of 100KHz 18GHz wide-band and stability thereof.

Description

A kind of electromagnetic shielding structural conductive silicone rubber and preparation

Technical field

The invention belongs to conductive polymer composite, relate to one and there is in wide frequency range good electrical magnetic cup Cover structural conductive silicone rubber and the preparation method of performance, can be applicable to electromagnetic shielding field.

Background technology

Along with the fast development of modern science and technology, electronic and electrical equipment is constantly to integrated and miniaturization direction Development, the EMI harm thus brought is the most serious.Conductive silicon rubber can be inhaled by generation as one Receive or reflection loss effectively weakens or suppresses the compound elastomer of EMI harm to become a kind of new Emerging electromagnetic shielding material.

Conductive silicon rubber is by the most mixed with macromolecule silicone rubber and other auxiliary agents for one or more packing materials Close, the rubber product that extruded molding or injection moulding method process.The conductive silicon rubber occurred the earliest Glue is prepared from using argentum powder as filler, and this type of composite has leading of excellence due to the addition of silver Electrical property.The June 29 nineteen ninety United States Patent (USP) US5075038(applying date, publication date 1991 12 The moon 24) disclose a kind of composite powder being coated with argentum powder or silver conductive silicon rubber as filler, it has Well electric conductivity and heat stability, can play the work of current lead-through while two components and parts are fixed in connection With.But this type of material is filled with mass filler (75wt.% argentum powder) to improve electric conductivity, and as filling out The argentum powder of material belongs to precious metal, thus results in production cost high.The patent CN102220012A(applying date: On June 8th, 2011, publication date: on October 19th, 2011) by containing vinylpolydimethyl silica The rubber matrix of alkane adds 52～67% silver-coated copper powder and 3～18% silvered glass fiber obtain a kind of one-component Conductive rubber material.It vulcanizes at a temperature of 65～135 DEG C, body resistivity≤0.004 Ω cm, electromagnetic shielding Usefulness in 20MHz～2GHz frequency range >=80dB.But, the packing material of this composite is still filled out in silver system In the range of material, even if reduce loading by the way of fiber adulterates as far as possible, but proportion of filler still accounts for overall material The 70wt.% of material, causes production cost to improve.

In order to reduce cost, each relevant enterprise have developed all kinds of compound powder filler successively and fills out to substitute silver system Material.The United States Patent (USP) US5910524(applying date: on October 6th, 1997, publication date: in June, 1999 8 days) disclose a kind of conducing composite material with nickel coated graphite powder as filler, its matrix is the silicon containing vinyl Oxygen alkane resin, hydrogeneous siloxanes and the mixture of platinum catalyst.The composite that this single filler is filled Specific insulation is 0.5-1 Ω cm, and electric conductivity is unsatisfactory.Matrix is resin polymers, belongs to thermosetting Property material, does not possess rubber elastomer characteristics (such as sealing).The patent CN102276988A(applying date: 2011 On June 8, publication date: on December 14th, 2011) disclose subsequently a kind of (flat with nickel coated graphite powder All particle diameters are 50～100 μm) with nickel bag carbon fiber (a diameter of 7～10 μm, length 100～200 μm) for filling out Material, the heat cure conductive silicon compounded rubber that ethenyl blocking polydimethylsiloxane is matrix containing white carbon. Total loading of its Ni-C filler is at 65～67.1wt.% scopes (original text: 52.5-62.5 weight portion contains white carbon Ethenyl blocking polydimethylsiloxane；37.5-47.5 the low viscosity ethenyl blocking poly dimethyl of weight portion Siloxanes；The Ni-C conductive filler of 195-210 weight portion particle diameter 7 μm-200 μm；0.1-0.15 weight portion alkynes Alcohol inhibitor；The linear methylhydrogenpolysi,oxane cross-linking agent of 2.8-3.2 weight portion Si-H base, hydrogen-based percent mass Compare 0.4-0.8%；This special platinum catalyst of the karr of 0.1-0.2 weight portion, Pt content 3000-5000ppm；0.05-1 The thixotropic agent of weight portion) in, belonging to in-place forming conductive rubber, body resistivity is in 0.05～0.1 Ω cm scope In.This composite increases conductive path by filling nickel bag carbon fiber in nickel coated graphite powder, reduces body Resistivity and filler addition.But this patent does not report its parameter index in terms of electromagnetic shielding, therefore Preparing this composite according to open formula in this patent, and it is carried out electromagnetic shielding test, result is shown in tool Experimental data (comparative example 2) in body embodiment.

The patent CN101503534A(applying date: on March 2nd, 2009, publication date: August 12 in 2009 Day) disclose a kind of conducing composite material being improved shielding properties by the doping of multiple filler.This material Matrix is butyl rubber, and filler is homemade magnesium alloy powder and the ferrite particle of polyaniline-coated, incite somebody to action both Uniform stirring and with sulfur 155 DEG C carry out sulfuration prepare.The composite shielding effect that this patent embodiment 1 prepares Can be up to 79.5-96.3dB.But, magnesium alloy powder is necessarily drawn to metal Al, Mg, Cu, Zn, Sn Melting cut into 2～5mm powder under the protective atmosphere of SF6；Polyaniline-coated ferrite needs mix Diluent dispersion ferrite, immerses polyaniline-acrylic coating after alkali cleaning, pickling and dried, After carry out dried prepare.Therefore, the complicated process of preparation of this composite, it is unfavorable for high-volume industry Produce.

In addition to above by selecting different filler to increase the loss to electromagnetic wave, it is also possible to tie from product Structure angle manages to improve shielding properties.At present, product conductive rubber carrying out structure design is mainly applied In electromagnetic shielding sealing ring and the tire art of motor vehicles.

The United States Patent (USP) US6410846(applying date: on December 14th, 1999, publication date: in July, 2002 25 days) disclose a kind of layer structure electromagnetic shielding sealing strip that two kinds of elastomeric materials are replaced superposition composition, It is mainly used in the sealing of electronic product I/O substrate.The matrix of this composite is thermosetting silicon materials or thermoplastic Property silicon materials, filler is argentum powder.The first elastomeric material directly vulcanizes matrix and prepares, the second elastomeric material Matrix mixes sulfuration with filler prepare.Stratified material is obtained by alternately superposition both materials, additionally, Also the first material is cut out opening, in order to the embedding of electrical connector.Selecting this structure is to protect Filler is saved while card electric conductivity.But this composite filler is expensive argentum powder, and matrix is thermoplastic Sex vesicle foam or thermosetting silicon materials, and its special structure is for specific application scenario.

The United States Patent (USP) US6172155(applying date: on October 24th, 1998, publication date: January calendar year 2001 9 days) disclose the automobile tire preparation technology of a kind of double-layer structure, and to indicate be by carbon fiber, white carbon black, gold Conductive layer and insulating barrier laminar manner after Compound Extrusion or first extruding that the conductive fillers such as metal particles are filled prepare 's.This material can effectively eliminate the motor vehicles internal electrostatic charge produced and interference in operation process, it is to avoid Impact that human body is brought by electrostatic impact and harm.Meanwhile, this structure can reduce the usage amount of conductive filler, Cost-effective.But this patent uses solid rubber as matrix, and more pay close attention to elimination electrostatic with And raising mechanical property, do not study for capability of electromagnetic shielding, so this composite is merely retained in Conduction between car body and ground.

The patent CN102501460A(applying date: on October 31st, 2011, publication date: in June, 2012 20 days) disclose and a kind of be applicable to conductive material, electromagnetic shielding material or the multiple structure of button conductive component Rubber conductive plate and conductive particle, by conductive layer (0.01 μm～the foil of 1mm or the coat of metal), mistake Cross layer (1 μm～the thin polymer film of 1mm or foil) and elastic layer (0.1mm～10mm rubber sheet) Composition.The connection of interlayer can use mechanical pressure to be combined, hot melt is compound, vacuum-sintering is compound, gluing compound Or by changing layer surface chemistry polarity or chemical composition method.This patent Example 2 material can be used for electromagnetism Shielding field, is by the netted copper foil of 0.1mm, 0.5mm Kapton and 3mm rubber and plastic sheet Material and thin polymer film are formed by macromolecular adhesive bonding.This material contains metal sheet, polymer The various material such as thin film, adhesive, elastomer, each layer is homogenous material, by simple folded structures system For forming.Due to this sandwich acts primarily as conduction or shielding action be by the coat of metal or thin slice The conductive layer constituted, its toughness is poor, therefore cracky under stress condition.Once this layer of breakage, its electricity Magnetic shield performance can be greatly affected, and is not therefore suitable for the environment such as pressurized, carrying.Additionally, this patent Do not report out electric conductivity and the capability of electromagnetic shielding parameter of this multilayer material.

In addition to the patent announced, current Chinese scholars has also been carried out much by changing material structure Improve the research of shielding properties.Shailaja Pande et al. (Improved Electromagnetic Interference Shielding Properties of MWCNT-PMMA Composites Using Layered Structures.Nanoscale Res Lett.2009,4:327-334.) with polymetylmethacrylate be Matrix, multi-walled carbon nano-tubes MWCNT is as packing material, by solvent cast and compression-moulding methods system For double-deck and the composite of seven layers.In 8.2GHz-12.4GHz frequency range, 7 layers of composite Shield effectiveness is 40dB, and double layer material is only 30dB, and in the situation that thickness is constant, the raising of the number of plies is screen Cover usefulness and add 10dB.But filler used by this kind of material still belongs to the laboratory exploratory stage, and obtained Composite is thermosets, does not possess rubber elastomer characteristics, is not suitable for the pressurized environment such as sealing.Chunyu Wei et al. (Double-layer microwave absorber based on nanocrystalline Zn0.5Ni0.5Fe2O4/ α-Fe microfibers.Mater Design.2012,35:363-368.) it is prepared for one to receive The brilliant Zn of rice_0.5Ni_0.5Fe₂O₄With the double-deck Wave suction composite material that carbonyl iron fibres is filler, matrix is paraffin.Stone Waxiness is soft, belongs to non-structural material, may not apply under force environment using it as the composite of matrix, With less rubber elastomer characteristics.Although additionally, this composite is at 2-18GHz scope shield effectiveness peak Up to 75dB, but its shield effectiveness variation tendency parabolically shape, shield effectiveness minima is only at about 5dB. Therefore, this composite can not meet wide frequency range and is respectively provided with good shield effectiveness.

Comprehensive the above, the problem existing for current conductive silicon rubber patent includes: (1) selects noble metal It is that filler causes production cost to improve；(2) in the case of material structure is single, in order to reach preferably to lead Electrical property, needs the biggest filler loading, and during the doping of multiple self-made fill, the preparation of filler makes whole Complicated process of preparation；(3) interlayer of the structural material made by multiple homogenous material superposition is even Connect complex process, play conductive layer (foil or the coat of metal) poor toughness of major function effect, uncomfortable Close force environment；(4) material system of metal-polymer class formation type composite many with thermosets or Paraffin is matrix, does not possess rubber elastomer characteristics, even can not play compression seal effect.

Summary of the invention

The present invention is directed to the technical problem that presently, there are, it is provided that a kind of electromagnetic shielding being applicable to wide frequency range By structural conductive silicone rubber and preparation method thereof.

Electromagnetic shielding structural conductive silicone rubber provided by the present invention, it is characterised in that this material uses Bilayer or the conductive silicon rubber composite of multiple structure, and it is coated with one layer of base glue as insulating sticky at interlayer Layer, forms a kind of " sandwich " structure, and the raw material composition of its conductive silicon rubber composite is by weight percentage: (1) 59～the packing material of 64wt.%, such as nickel coated graphite powder, Al contained Ni, nikel powder etc.；(2) 34～39wt.% The silicone rubber matrix containing vinyldimethicone of end-blocking；(3) 0.01～the inhibitor of 0.05wt.%； (4) 1～the cross-linking agent of 3wt.%；(5) 0.1～the catalyst of 0.2wt.%.Base glue former as insulation adhesion coating Material composition is by the silicone rubber containing vinyldimethicone of the end-blocking in conductive silicon rubber composite The composition of matrix, inhibitor, cross-linking agent and catalyst, and its quality compositing range also with conductive silicon rubber The silicone rubber matrix containing vinyldimethicone of the end-blocking in composite, inhibitor, cross-linking agent Identical with the compositing range of catalyst.

Concrete each electromagnetic shielding structural conductive silicone rubber, its double-deck or conductive silicon rubber of multiple structure Glue composite is identical or different.

The thickness of every layer of conductive silicon rubber composite is 0.5～4mm, the thickness≤0.1mm of insulation adhesion coating.

The preparation method of electromagnetic shielding structural conductive silicone rubber provided by the present invention, it is characterised in that Comprise the following steps:

(1) in blender or rubber mixing machine, the rubber containing vinyldimethicone is added according to above-mentioned formula Gum base body, at a temperature of 25～35 DEG C add inhibitor stir 10～60 minutes, be sequentially added into subsequently cross-linking agent, Catalyst continuous stirring 10 the most under vacuum conditions～make base glue for 30 minutes, evacuation ensures and atm difference ≥0.09MPa；

(2) in blender or rubber mixing machine, put into the prepared base glue of step (1) and packing material first stirs 10～30 Minute, then 10～30 minutes prepared conductive silicon rubber mixture of stirring under vacuum conditions, stir in the process Mixing ambient temperature and control in the range of 15～35 DEG C, evacuation ensures and atm difference >=0.09MPa；

(3) conductive silicon rubber mixture step (2) prepared is by extruded method sulfuration plastic Sheet, curing temperature can select in the range of 150～200 DEG C according to execution conditions, cure time 3～10min, sulfur Change pressure 1～30MPa；

(4) will according to step (3) prepare two panels or multi-disc thickness and packing material can identical can be different lead Electricity silicone rubber sheet material carries out bonding compound, is positioned in the extrusion molding dies of desired thickness, adjacent two lamellas Add abundant step (1) between conductive silicon rubber sheet and prepare base glue, under the sulfide stress of 1～30MPa Place the 10～60s unnecessary insulating cements of extrusion, recover normal pressure subsequently and at a temperature of 80～130 DEG C, place 1 10min, takes out.

Inhibitor in above-mentioned steps (1) is preferably acetylene Hexalin.

Cross-linking agent in above-mentioned steps (1) is preferably linear methyl hydrogen polysiloxanes, containing vinylpolydimethyl Siloxanes viscosity (25 DEG C) is 1000～20000mPa s, hydrogen-based mass content 0.4-0.8%.

Catalyst in above-mentioned steps (1) is preferably this special platinum catalyst of karr, platinum content 3000-5000ppm.

Packing material in above-mentioned steps (2) can be that cladded type conductive filler is (such as nickel content 40～80wt.% nickel Bag graphite powder, the Al contained Ni etc. of nickel content 20～60wt.%), monometallic powder or alloy powder be (such as particle diameter Be 1～200 μm nikel powders, FeNi powders etc.) in one or more.

Inventive principle

For applying at the conductive silicon rubber of wide frequency range, it is intended in high frequency, medium and low frequency electromagnetic field There is good shielding properties.In high-frequency range, mostly conductive silicon rubber is to be come by excellent electric conductivity Realize shielding action.The most intensive complexity of conductive network of conductive silicon rubber, electric conductivity is the best, at electromagnetism The eddy-current loss produced in Chang is the biggest, and shielding properties is the best.It is theoretical theoretical with tunnel-effect according to conductive channel, The grain spacing of conductive silicon rubber is the key factor determining conductive network density.At present, mostly composite is Shorten grain spacing by interpolation threadiness, lamellar, dendritic fillers, but filler pattern is the most complicated, its Mobility when mixing with matrix is the poorest, causes mixing uneven.But from sulfuration process, use 150～200 DEG C curing temperature can improve crosslink material density, make matrix network shrink, thus shorten grain spacing, increase Add the conductive path quantity formed because there is tunnel-effect, and then carry in the case of identical filler loading High electric conductivity.

But when electromagnetic field frequency reduces, and eddy current effect weakens the most therewith, this reduces and is caused by eddy-current loss Shielding action.Therefore, for medium and low frequency shielding electromagnetic waves, except setting about in terms of material, also can be from Increase loss on material structure, improve shield effectiveness.Theoretical according to S.A.Schelkunoff electromagnetic shielding, electricity Magnetic shield usefulness is considered as electromagnetic wave the loss sum, i.e. absorption loss, reflection loss of three kinds of different mechanism And multipath reflection loss.Absorption loss occurs in shield, is the dipole in shielding material and electromagnetic field Loss caused by effect, eddy-current loss is exactly electric dipole and the result of electromagnetic field effect in filler；Multiple Reflection loss refer to when electromagnetic wave wear from shield surface be mapped to another surface time, part electromagnetic wave energy can be anti- It is emitted back towards in shield, and the loss caused at shielding intrabed multiples, general when absorption loss is more than 10dB Time negligible；And reflection loss is owing to air does not mate caused with the natural impedance on shield surface. Electromagnetic wave is in communication process, if the impedance of propagation medium changes, electromagnetic wave will be sent out at change interface Raw reflection.Utilize this characteristic, conductive silicon rubber is made bilayer or multiple structure and interlayer increases insulating cement Layer, makes to occur twice in conductive silicon rubber system or repeatedly impedance variation.When in electromagnetic wave propagation to material, Reflect at interlayer.Compared with the conductive silicon rubber of non-structure design, structural material has identical whirlpool Also add one or many reflection loss while stream loss, this provides for improved total shielding properties of material.

The structural conductive silicone rubber prepared by the technique using the present invention is ensureing that General Mechanics performance is wanted While asking, the shield effectiveness in the range of 100KHz-18GHz wide-band and stable performance thereof can be effectively improved Property.

This material has the following characteristics that (1) has saved filler loading by the adjustment of sulfuration process, saves Production cost；(2), while there is good electrical magnetic shield performance under ensureing high frequency, improve medium and low frequency model The shielding properties enclosed, is respectively provided with the requirement of good shield effectiveness in can meeting wide frequency range；(3) preparation technology Simply.The composite of this patent only include matrix and the mixing of filler, every layer of conductive silicon rubber sulfuration with And bonding compound three big steps, it is not necessary to filler carries out pretreatment, and interlayer Joining Technology is single, improves production Efficiency；(4) capability of electromagnetic shielding requirement can be met, possess again preferable mechanical property.

Detailed description of the invention

The embodiment that the present invention is enumerated is only used as use of the present invention is described, the protection of the present invention is with claims Description is as the criterion.

Embodiment 1:

Filler: preferably nickel coated graphite powder (Ni-C), nickel content 40～80wt.%.

First, in the 600g rubber matrix containing ethenyl blocking polydimethylsiloxane, it is separately added into acetylene ring This special platinum catalyst 2.0g of hexanol inhibitor 0.3g, methylhydrogenpolysi,oxane cross-linking agent 25g, karr, 25～35 Stirring 20 minutes prepared base glue at a temperature of DEG C, evacuation ensures pressure reduction >=0.09MPa.Secondly, 1078g is added Nickel coated graphite powder (63.2wt.%), stirring 5 minutes, are stirred for 5 the most under vacuum conditions the most at ambient pressure Minute, whipping temp is room temperature, and evacuation ensures pressure reduction >=0.09MPa.Then, 185 DEG C of curing temperatures are used Conductive silicon rubber is sulfided into the thick print of 1mm.Finally, two panels 1mm thickness sample is stacked in 2mm thick Extrusion molding dies in, interlayer add base glue.10s extrusion is placed unnecessary under the sulfide stress of 10MPa Base glue, recovers normal pressure subsequently and vulcanizes 3min at a temperature of 125 DEG C, taking out.

Embodiment 2:

Filler: preferably nickel coated graphite powder (Ni-C), nickel content 40～80wt.%.

First, in the 600g rubber matrix containing ethenyl blocking polydimethylsiloxane, it is separately added into acetylene ring This special platinum catalyst 2.0g of hexanol inhibitor 0.3g, methylhydrogenpolysi,oxane cross-linking agent 25g, karr, 25～35 Stirring 20 minutes prepared base glue at a temperature of DEG C, evacuation ensures pressure reduction >=0.09MPa.Secondly, 940g is added Nickel coated graphite powder (60.0wt.%), stirring 5 minutes, are stirred for 5 the most under vacuum conditions the most at ambient pressure Minute, whipping temp is room temperature, and evacuation ensures pressure reduction >=0.09MPa.Then, 185 DEG C of curing temperatures are used Conductive silicon rubber is sulfided into 0.9～1mm thick print.Finally, four 0.9～1mm thickness samples are stacked in In the extrusion molding dies that 4mm is thick, interlayer adds base glue.Under the sulfide stress of 10MPa, place 10s squeeze Go out many complementary basis glue, recover normal pressure subsequently and at a temperature of 125 DEG C, vulcanize 3min, taking out.

Embodiment 3:

Filler: preferably nickel coated graphite powder (Ni-C), nickel content 40～80wt.%.

First, in the 700g rubber matrix containing ethenyl blocking polydimethylsiloxane, it is separately added into acetylene ring This special platinum catalyst 4.0g of hexanol inhibitor 0.3g, methylhydrogenpolysi,oxane cross-linking agent 25g, karr, 25～35 Stirring 20 minutes prepared base glue at a temperature of DEG C, evacuation ensures pressure reduction >=0.09MPa.Secondly, 1296g is added Nickel coated graphite powder (63.9wt.%), stirring 5 minutes, are stirred for 5 the most under vacuum conditions the most at ambient pressure Minute, whipping temp is room temperature, and evacuation ensures pressure reduction >=0.09MPa.Then, 185 DEG C of curing temperatures are used Conductive silicon rubber is sulfided into the thick print of the thick and a piece of 2mm of two panels 0.5mm.Finally, three samples are folded Being put in the thick extrusion molding dies of 3mm, interlayer adds base glue.Place under the sulfide stress of 10MPa 10s extrudes many complementary basis glue, recovers normal pressure subsequently and vulcanizes 3min at a temperature of 125 DEG C, taking out.

Embodiment 4:

Filler: preferably Al contained Ni (Ni-Al), nickel content 20～60wt.%.

First, in the 600g rubber matrix containing ethenyl blocking polydimethylsiloxane, it is separately added into acetylene ring This special platinum catalyst 3.0g of hexanol inhibitor 0.45g, methylhydrogenpolysi,oxane cross-linking agent 25g, karr, 25～35 Stirring 60 minutes prepared base glue at a temperature of DEG C, evacuation ensures pressure reduction >=0.09MPa.Secondly, 956g is added Al contained Ni (60.3wt.%), stirring 5 minutes, are stirred for 10 the most under vacuum conditions the most at ambient pressure Minute, whipping temp is room temperature, and evacuation ensures pressure reduction >=0.09MPa.Then, 160 DEG C of curing temperatures are used Conductive silicon rubber is sulfided into 0.9～1mm thick print.Finally, two panels 0.9～1mm thickness sample is stacked in In the extrusion molding dies that 2mm is thick, interlayer adds base glue.Under the sulfide stress of 10MPa, place 20s squeeze Go out many complementary basis glue, recover normal pressure subsequently and at a temperature of 80 DEG C, vulcanize 10min, taking out.

Embodiment 5:

Filler: preferably Al contained Ni (Ni-Al), nickel content 20～60wt.%.

First, in the 600g rubber matrix containing ethenyl blocking polydimethylsiloxane, it is separately added into acetylene ring This special platinum catalyst 3.0g of hexanol inhibitor 0.45g, methylhydrogenpolysi,oxane cross-linking agent 25g, karr, 25～35 Stirring 60 minutes prepared base glue at a temperature of DEG C, evacuation ensures pressure reduction >=0.09MPa.Secondly, 1029g is added Al contained Ni (62.1wt.%), stirring 5 minutes, are stirred for 10 the most under vacuum conditions the most at ambient pressure Minute, whipping temp is room temperature, and evacuation ensures pressure reduction >=0.09MPa.Then, 160 DEG C of curing temperatures are used Conductive silicon rubber is sulfided into the thick print of 2mm.Finally, two panels 2mm thickness sample is stacked in 4mm thick Extrusion molding dies in, interlayer add base glue.20s extrusion is placed unnecessary under the sulfide stress of 10MPa Base glue, recovers normal pressure subsequently and vulcanizes 10min at a temperature of 80 DEG C, taking out.

Embodiment 6:

Filler: nikel powder (Ni).

First, in the 600g rubber matrix containing ethenyl blocking polydimethylsiloxane, it is separately added into acetylene ring This special platinum catalyst 3.5g of hexanol inhibitor 0.5g, methylhydrogenpolysi,oxane cross-linking agent 40g, karr, 25～35 Stirring 45 minutes prepared base glue at a temperature of DEG C, evacuation ensures pressure reduction >=0.09MPa.Secondly, 1030g is added Nikel powder (61.5wt.%), stirring 10 minutes, are stirred for 20 minutes the most under vacuum conditions the most at ambient pressure, Whipping temp is room temperature, and evacuation ensures pressure reduction >=0.09MPa.Then, 200 DEG C of curing temperatures are used to conduct electricity Silicon rubber vulcanization becomes the print that 1mm is thick.Finally, two panels 1mm thickness sample is stacked in the thick extruding of 2mm In mould, interlayer adds base glue.Under the sulfide stress of 10MPa, place 10s extrude many complementary basis glue, Recover normal pressure subsequently and at a temperature of 100 DEG C, vulcanize 10min, taking out.

Embodiment 7:

Filler: nikel powder (Ni).

First, in the 600g rubber matrix containing ethenyl blocking polydimethylsiloxane, it is separately added into acetylene ring This special platinum catalyst 3.5g of hexanol inhibitor 0.5g, methylhydrogenpolysi,oxane cross-linking agent 40g, karr, 25～35 Stirring 45 minutes prepared base glue at a temperature of DEG C, evacuation ensures pressure reduction >=0.09MPa.Secondly, 1056g is added Nikel powder (62.1wt.%), stirring 10 minutes, are stirred for 20 minutes the most under vacuum conditions the most at ambient pressure, Whipping temp is room temperature, and evacuation ensures pressure reduction >=0.09MPa.Then, 200 DEG C of curing temperatures are used to conduct electricity Silicon rubber vulcanization becomes the print that 1mm is thick.Finally, three 1mm thickness samples are stacked in the thick extruding of 3mm In mould, interlayer adds base glue.Under the sulfide stress of 10MPa, place 10s extrude many complementary basis glue, Recover normal pressure subsequently and at a temperature of 100 DEG C, vulcanize 10min, taking out.

Comparative example 1:

Contrasting with embodiment 1, filler is preferred nickel coated graphite powder (Ni-C), nickel content 40～80wt.%.

First, in the 600g rubber matrix containing ethenyl blocking polydimethylsiloxane, it is separately added into acetylene ring This special platinum catalyst 2.0g of hexanol inhibitor 0.3g, methylhydrogenpolysi,oxane cross-linking agent 25g, karr, 25～35 Stirring 20 minutes prepared base glue at a temperature of DEG C, evacuation ensures pressure reduction >=0.09MPa.Secondly, 1078g is added Nickel coated graphite powder (63.2wt.%), stirring 5 minutes, are stirred for 5 the most under vacuum conditions the most at ambient pressure Minute, whipping temp is room temperature, and evacuation ensures pressure reduction >=0.09MPa.Finally, conductive silicon rubber is placed in 2mm In mould, use 185 DEG C of curing temperatures that mixture is sulfided into the thick print of 2mm, take out.

Comparative example 2:

Contrasting with embodiment 1, filler is preferred nickel coated graphite powder (Ni-C), according to patent The 2mm thickness single layer samples that CN102276988A step prepares.

Comparative example 3:

Double-deck with embodiment 4() contrast.Filler is preferred Al contained Ni (Ni-Al), nickel content 20～60 wt.%。

First, in the 600g rubber matrix containing ethenyl blocking polydimethylsiloxane, it is separately added into acetylene ring This special platinum catalyst 3.0g of hexanol inhibitor 0.45g, methylhydrogenpolysi,oxane cross-linking agent 25g, karr, 25～35 Stirring 60 minutes prepared base glue at a temperature of DEG C, evacuation ensures pressure reduction >=0.09MPa.Secondly, 956g is added Al contained Ni (60.3wt.%), stirring 5 minutes, are stirred for 10 the most under vacuum conditions the most at ambient pressure Minute, whipping temp is room temperature, and evacuation ensures pressure reduction >=0.09MPa.Finally, conductive silicon rubber is placed in 2mm In mould, use 185 DEG C of curing temperatures that mixture is sulfided into the thick print of 2mm, take out.

Comparative example 4:

Contrasting with embodiment 6, filler is nikel powder (Ni).

First, in the 600g rubber matrix containing ethenyl blocking polydimethylsiloxane, it is separately added into acetylene ring This special platinum catalyst 3.5g of hexanol inhibitor 0.5g, methylhydrogenpolysi,oxane cross-linking agent 40g, karr, 25～35 Stirring 45 minutes prepared base glue at a temperature of DEG C, evacuation ensures pressure reduction >=0.09MPa.Secondly, 1030g is added Nikel powder (61.5wt.%), stirring 10 minutes, are stirred for 20 minutes the most under vacuum conditions the most at ambient pressure, Whipping temp is room temperature, and evacuation ensures pressure reduction >=0.09MPa.Finally, conductive silicon rubber is placed in 2mm mould In tool, use 200 DEG C of curing temperatures that mixture is sulfided into the thick print of 2mm, take out.

Experimental data:

Following table is the index parameter of conductive rubber composite material.

Knowable to upper table data, identical at filling kind, but in the case of filler loading and formula all differences, Embodiment 1 sample containing 63wt.% filler under 100KHz～100MHz frequency range ratio containing 67wt.% filler Patent sample (comparative example 2) high 6～17dB.

Additionally, in the case of composite-material formula is identical, embodiment 1 sample is in 20MHz～2GHz frequency range Lower shield effectiveness is than comparative example 1 sample high 18～31dB；Embodiment 4 sample is in 100KHz～18GHz frequency range Under shield effectiveness than comparative example 3 sample high 10～30dB；Embodiment 6 sample is at 100KHz～100MHz Shield effectiveness under frequency range is than comparative example 4 high about the 10dB of sample.Therefore, the sample carrying out structure design can It is effectively improved the capability of electromagnetic shielding of composite, is especially less than the medium and low frequency feelings of 2GHz when wave frequency Under condition, its electromagnet shield effect is apparently higher than single layer of conductive rubber composite.

Claims (9)

1. electromagnetic shielding structural conductive silicone rubber, it is characterised in that electromagnetic shielding structural conductive silicon Rubber uses the double-deck or conductive silicon rubber composite of multiple structure, and is coated with one layer of base glue work at interlayer For insulation adhesion coating, form " sandwich " structure, the raw material composition by weight hundred of its conductive silicon rubber composite Proportion by subtraction is: (1) 59～the packing material of 64wt.%, the end-blocking of (2) 34～39wt.% containing the poly-diformazan of vinyl The silicone rubber matrix of radical siloxane；(3) 0.01～the inhibitor of 0.05wt.%；(4) 1～the cross-linking agent of 3wt.%； (5) 0.1～the catalyst of 0.2wt.%；Raw material composition as the base glue of insulation adhesion coating is multiple by conductive silicon rubber The silicone rubber matrix containing vinyldimethicone of the end-blocking in condensation material, inhibitor, cross-linking agent and The composition of catalyst, and its quality composition with conductive silicon rubber composite in end-blocking containing vinyl gather The silicone rubber matrix of dimethyl siloxane, inhibitor, cross-linking agent are identical with the compositing range of catalyst；

Packing material in above-mentioned (1) is in cladded type conductive filler, monometallic powder or alloy powder Plant or several；

Electromagnetic shielding structural conductive silicone rubber described above uses the method for following steps to prepare:

(1) in blender or rubber mixing machine, the silicon containing vinyldimethicone is added according to above-mentioned formula Rubber matrix, at a temperature of 25～35 DEG C add inhibitor stir 10～60 minutes, be sequentially added into subsequently cross-linking agent, Catalyst, the most under vacuum conditions continuous stirring 10～make base glue for 30 minutes, evacuation ensures and air Pressure reduction >=0.09MPa；

(2) in blender or rubber mixing machine, put into the prepared base glue of step (1) and packing material first stirs 10～30 Minute, then 10～30 minutes prepared conductive silicon rubber mixture of stirring under vacuum conditions, stir in the process Mixing ambient temperature and control in the range of 15～35 DEG C, evacuation ensures and atm difference >=0.09MPa；

(3) conductive silicon rubber mixture step (2) prepared is by extruded method sulfuration plastic Sheet, curing temperature can select in the range of 150～200 DEG C according to execution conditions, cure time 3～10min, sulfur Change pressure 1～30MPa；

(4) by the two panels prepared according to step (3) or multi-disc thickness and identical or different the leading of packing material Electricity silicone rubber sheet material carries out bonding compound, is positioned in the extrusion molding dies of desired thickness, adjacent two lamellas The base glue that abundant step (1) prepares is added, at the sulfide stress of 1～30MPa between conductive silicon rubber sheet Lower placement 10～60s extrusion many complementary basis glue, subsequently recover normal pressure and at a temperature of 80～130 DEG C place 1～ 10min, takes out.

2. according to the electromagnetic shielding structural conductive silicone rubber of claim 1, it is characterised in that each Electromagnetic shielding structural conductive silicone rubber, its double-deck or multiple structure conductive silicon rubber composite is identical Or difference.

3. according to the electromagnetic shielding structural conductive silicone rubber of claim 1, it is characterised in that lead for every layer The thickness of electricity silicon rubber composite material is 0.5～4mm.

4. according to the electromagnetic shielding structural conductive silicone rubber of claim 1, it is characterised in that insulating sticky Thickness≤the 0.1mm of layer.

5. according to the electromagnetic shielding structural conductive silicone rubber of claim 1, it is characterised in that inhibitor For acetylene Hexalin.

6. according to the electromagnetic shielding structural conductive silicone rubber of claim 1, it is characterised in that cross-linking agent For linear methyl hydrogen polysiloxanes.

7. according to the electromagnetic shielding structural conductive silicone rubber of claim 1, it is characterised in that catalyst For this special platinum catalyst of karr, platinum content 3000-5000ppm.

8. according to arbitrary electromagnetic shielding structural conductive silicone rubber of claim 1-7, it is characterised in that Packing material is nickel content 40～80wt.% nickel coated graphite powder, the Al contained Ni of nickel content 20～60wt.%, nickel One or more in powder or FeNi powders.

9. the method for the preparation arbitrary electromagnetic shielding structural conductive silicone rubber described in claim 1-7, its It is characterised by, comprises the following steps:

(1) in blender or rubber mixing machine, the silicon containing vinyldimethicone is added according to above-mentioned formula Rubber matrix, at a temperature of 25～35 DEG C add inhibitor stir 10～60 minutes, be sequentially added into subsequently cross-linking agent, Catalyst, the most under vacuum conditions continuous stirring 10～make base glue for 30 minutes, evacuation ensures and air Pressure reduction >=0.09MPa；

(2) in blender or rubber mixing machine, put into the prepared base glue of step (1) and packing material first stirs 10～30 Minute, then 10～30 minutes prepared conductive silicon rubber mixture of stirring under vacuum conditions, stir in the process Mixing ambient temperature and control in the range of 15～35 DEG C, evacuation ensures and atm difference >=0.09MPa；

(3) conductive silicon rubber mixture step (2) prepared is by extruded method sulfuration plastic Sheet, curing temperature can select in the range of 150～200 DEG C according to execution conditions, cure time 3～10min, sulfur Change pressure 1～30MPa；

(4) by the two panels prepared according to step (3) or multi-disc thickness and identical or different the leading of packing material Electricity silicone rubber sheet material carries out bonding compound, is positioned in the extrusion molding dies of desired thickness, adjacent two lamellas The base glue that abundant step (1) prepares is added, at the sulfide stress of 1～30MPa between conductive silicon rubber sheet Lower placement 10～60s extrusion many complementary basis glue, subsequently recover normal pressure and at a temperature of 80～130 DEG C place 1～ 10min, takes out.