CN103496228A - Structural conductive silicone rubber for electromagnetic shielding and preparation - Google Patents
Structural conductive silicone rubber for electromagnetic shielding and preparation Download PDFInfo
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- CN103496228A CN103496228A CN201310385127.5A CN201310385127A CN103496228A CN 103496228 A CN103496228 A CN 103496228A CN 201310385127 A CN201310385127 A CN 201310385127A CN 103496228 A CN103496228 A CN 103496228A
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Abstract
The invention discloses a structural conductive silicone rubber for electromagnetic shielding and preparation, and belongs to the technical field of conductive polymer composites. The conductive silicone rubber composite is a double-layer or multi-layer structure, and interlamination is coated with a layer of a base rubber as an insulating bonding layer, and the conductive silicone rubber composite comprises conductive powder, a silicone rubber matrix containing vinyl polydimethylsiloxane, an alkynol inhibitor, a platinum catalyst and a crosslinking agent. The prepared structural conductive silicone rubber can ensure general mechanical performance requirements, and meanwhile can effectively improve the shielding effectiveness and performance stability of a 100KHz-18GHz broadband segment range.
Description
Technical field
The invention belongs to conductive polymer composite, relate to a kind of structural conductive silicon rubber and preparation method who there is the good electrical magnetic shield performance in wide frequency range, can be applicable to the electromagnetic shielding field.
Background technology
Along with the fast development of modern science and technology, electronic and electrical equipment is constantly to integrated and microminiaturized future development, and the electromagnetic interference of bringing thus harm is day by day serious.Conductive silicon rubber can become by the compound elastomer that generation absorbs or reflection loss effectively weakens or the inhibition electromagnetic interference endangers a kind of emerging electromagnetic shielding material at present as a kind of.
Conductive silicon rubber is that one or more packing materials and macromolecule silicon rubber and other auxiliary agents are fully mixed, the rubber product processed through extrusion molding or injection moulding method.The conductive silicon rubber occurred is the earliest usingd silver powder and is prepared from as filler, and this type of composite is owing to having excellent electric conductivity adding of silver.The 29 days June nineteen ninety applying date of U.S. Pat 5075038(, open day on December 24th, 1991) announced the conductive silicon rubber that a kind of composite powder of take silver powder or silver coating is filler, it has good electric conductivity and heat endurance, can when being connected and fixed two components and parts, play the effect of current lead-through.But materials has been filled mass filler (75wt.% silver powder) in order to improve electric conductivity, and belongs to precious metal as the silver powder of filler, therefore cause production cost high.The patent CN102220012A(applying date: on June 8th, 2011, open day: on October 19th, 2011) by containing adding 52～67% silver-coated copper powders in the rubber matrix of vinyldimethicone and 3～18% silvered glass fibers obtain a kind of one-component conductive rubber material.It vulcanizes at the temperature of 65～135 ℃, body resistivity≤0.004 Ω cm, electromagnet shield effect in 20MHz～2GHz frequency range >=80dB.But the packing material of this composite is still in the silver filler scope, even by the mode reduce loading of fiber doping, but proportion of filler still accounts for the 70wt.% of integral material, causes production cost to improve.
In order to reduce costs, each relevant enterprise has been developed all kinds of compound powder fillers successively to substitute silver filler.The U.S. Pat 5910524(applying date: on October 6th, 1997, open day: on June 8th, 1999) announced a kind of conducing composite material that nickel coated graphite powder is filler of take, its matrix was the silicone resin containing vinyl, hydrogeneous siloxanes and the mixture of platinum catalyst.The specific insulation of the composite that this single filler is filled is 0.5-1 Ω cm, and electric conductivity is unsatisfactory.Matrix is the resinae polymer, belongs to thermosets, does not possess rubber elastomer characteristics (as sealing).The patent CN102276988A(applying date: on June 8th, 2011, open day: on December 14th, 2011) disclose subsequently and a kind ofly take nickel coated graphite powder (average grain diameter is 50～100 μ m) (diameter is 7～10 μ m with nickel bag carbon fiber, length 100～200 μ m) be filler, the heat cure conductive silicon compounded rubber that the ethenyl blocking dimethyl silicone polymer that contains white carbon is matrix.(original text: the 52.5-62.5 weight portion is containing the ethenyl blocking dimethyl silicone polymer of white carbon in 65～67.1wt.% scope for total loading of its Ni-C filler; 37.5-47.5 the low viscosity ethenyl blocking dimethyl silicone polymer of weight portion; The Ni-C conductive filler of 195-210 weight portion particle diameter 7 μ m-200 μ m; 0.1-0.15 weight portion alkynol inhibitor; 2.8-3.2 the linear methylhydrogenpolysi,oxane crosslinking agent of weight portion Si-H base, hydrogen matrix amount percentage 0.4-0.8%; 0.1-0.2 the Ka Ersite platinum catalyst of weight portion, Pt content 3000-5000ppm; 0.05-1 the thixotropic agent of weight portion), belong to the in-place forming conductive rubber, body resistivity is in 0.05～0.1 Ω cm scope.This composite increases conductive path by admixture nickel bag carbon fiber in nickel coated graphite powder, reduces body resistivity and filler addition.But this patent is not reported its parameter index aspect electromagnetic shielding, so prepare this composite according to open formula in this patent, and it is carried out to the electromagnetic shielding test, the results are shown in the experimental data (Comparative Examples 2) in the specific embodiment.
The patent CN101503534A(applying date: on March 2nd, 2009, open day: on August 12nd, 2009) announced a kind of conducing composite material that adulterates to improve shielding properties by multiple filler.The matrix of this material is butyl rubber, and the ferrite particle that filler is homemade magnesium alloy powder and polyaniline-coated also vulcanizes both uniform stirrings to make at 155 ℃ with sulphur.The composite shield effectiveness that this patent example 1 makes can reach 79.5-96.3dB.But, the magnesium alloy powder need to be in proportion by metal A l, Mg, Cu, Zn, Sn melting cut into 2～5mm powder under the protective atmosphere of SF6; The polyaniline-coated ferrite need to disperse ferrite with mixed diluent, after alkali cleaning, pickling and dry the processing, immerses polyaniline-acrylic coating, finally carries out the drying processing and makes.Therefore, the complicated process of preparation of this composite, be unfavorable for industrial production in enormous quantities.
By selecting different fillers to increase electromagnetic loss, can also manage to improve shielding properties except above-mentioned from the product structure angle.At present, the product that conductive rubber is carried out to structural design is mainly used in the tire field of electromagnetic shielding sealing ring and motor vehicles.
The U.S. Pat 6410846(applying date: on December 14th, 1999, open day: on July 25th, 2002) announced a kind of layer structure electromagnetic shielding sealing strip that two kinds of elastomeric materials are alternately superposeed and form, be mainly used in the sealing of electronic product I/O substrate.The matrix of this composite is thermosetting silicon materials or thermoplasticity silicon materials, and filler is silver powder.The first elastomeric material directly vulcanizes matrix and makes, and the second elastomeric material mixes matrix sulfuration and makes with filler.Obtain stratified material by this bi-material that alternately superposes, in addition, also the first material will be cut out out to opening, so that the embedding of electrical connector.Selecting this structure is to save filler when guaranteeing electric conductivity.But this composite filler is expensive silver powder, matrix is thermoplastic foam or thermosetting silicon materials, and its special structure is for specific application scenario.
The U.S. Pat 6172155(applying date: on October 24th, 1998, open day: January 9 calendar year 2001) disclose a kind of automobile tire preparation technology of double-layer structure, and to indicate be that conductive layer and insulating barrier lamination mode after Compound Extrusion or first extruding of being filled by conductive fillers such as carbon fiber, carbon black, metallic particles makes.This material can effectively be eliminated motor vehicles inner electrostatic charge and interference produced in operation process, the impact of avoiding electrostatic impact to bring human body and harm.Simultaneously, this structure can reduce the use amount of conductive filler, cost-saving.But this patent adopts be solid rubber as matrix, and pay close attention to eliminate static and improve mechanical property more, for capability of electromagnetic shielding, do not studied, so the conduction that this composite only remains between car body and ground gets final product.
The patent CN102501460A(applying date: on October 31st, 2011, open day: on June 20th, 2012) disclose a kind of rubber conductive plate and conductive particle that is applicable to the sandwich construction of conductive material, electromagnetic shielding material or button conductive component, formed by conductive layer (sheet metal of 0.01 μ m～1mm or the coat of metal), transition zone (thin polymer film of 1 μ m～1mm or sheet metal) and elastic layer (0.1mm～10mm rubber sheet).The connection of interlayer can adopt that mechanical pressure is compound, hot melt is compound, vacuum-sintering is compound, gluing compound or by changing layer surface chemistry polarity or chemical composition method.These patent working example 2 materials can be used for the electromagnetic shielding field, are the netted copper foils by 0.1mm, and 0.5mm Kapton and 3mm rubber and plastic sheet material and thin polymer film form by macromolecule gluing agent bonding.This material has comprised the various material such as metal sheet, thin polymer film, adhesive, elastomer, and each layer is homogenous material, by simple structure stack, is prepared from.Due to what in this sandwich, mainly play conduction or shielding action, be the conductive layer consisted of the coat of metal or thin slice, its toughness is poor, therefore cracky under stress condition.Once this layer of breakage, its capability of electromagnetic shielding can be greatly affected, and therefore is not suitable for the environment such as pressurized, carrying.In addition, this patent is not reported out electric conductivity and the capability of electromagnetic shielding parameter of this multilayer material.
Except the patent of having announced, Chinese scholars has also been carried out the research that much by changing material structure, improves shielding properties at present.People (the Improved Electromagnetic Interference Shielding Properties of MWCNT-PMMA Composites Using Layered Structures.Nanoscale Res Lett.2009 such as Shailaja Pande, 4:327-334.) take polymetylmethacrylate as matrix, multi-walled carbon nano-tubes MWCNT, as packing material, has prepared composites double-deck and seven layers by solvent cast and compression-moulding methods.In the 8.2GHz-12.4GHz frequency range, the shield effectiveness of 7 layers of composite is 40dB, and double layer material is only 30dB, the constant situation at thickness, and the raising of the number of plies is that shield effectiveness has increased 10dB.But this kind of material filler used also belongs to the laboratory exploratory stage, and the composite obtained is thermosets, do not possess rubber elastomer characteristics, is not suitable for sealing and waits the pressurized environment.The people (Double-layer microwave absorber based on nanocrystalline Zn0.5Ni0.5Fe2O4/ α-Fe microfibers.Mater Design.2012,35:363-368.) such as Chunyu Wei have prepared a kind of with nanocrystalline Zn
0.5ni
0.5fe
2o
4with the double-deck Wave suction composite material that carbonyl iron fibres is filler, matrix is paraffin.Paraffin matter is soft, belongs to the unstructuredness material, usings its composite as matrix can not be applied to, under force environment, more not possess rubber elastomer characteristics.In addition, although this composite can reach 75dB at 2-18GHz scope shield effectiveness peak, its shield effectiveness variation tendency is parabolic shape, and the shield effectiveness minimum of a value is only in the 5dB left and right.Therefore, this composite can not meet wide frequency range and all has good shield effectiveness.
Comprehensive the above, the existing problem of conductive silicon rubber patent comprises at present: (1) selects noble metal is that filler causes production cost to improve; (2), in the situation that material structure is single, in order to reach desirable electric conductivity, need very large filler loading, and the preparation of filler makes whole complicated process of preparation during the doping of multiple self-made fill; (3) interlayer of the structural material of making by multiple homogenous material stack connects complex process, plays conductive layer (sheet metal or the coat of metal) poor toughness of major function effect, is not suitable for force environment; (4) material system of metal-polymer class formation type composite is matrix mainly with thermosets or paraffin, does not possess rubber elastomer characteristics, even can not play the compression seal effect.
Summary of the invention
The present invention is directed to the technical problem of current existence, a kind of structural conductive silicon rubber and preparation method thereof for electromagnetic shielding that is applicable to wide frequency range is provided.
Electromagnetic shielding provided by the present invention structural conductive silicon rubber, it is characterized in that, this material adopts the conductive silicon rubber composite of bilayer or sandwich construction, and be coated with one deck base glue as the insulation adhesion coating at interlayer, form a kind of " sandwich " structure, the raw material of its conductive silicon rubber composite forms: the packing material of (1) 59～64wt.%, as nickel coated graphite powder, Al contained Ni, nickel powder etc.; The silicon rubber matrix containing vinyldimethicone of the end-blocking of (2) 34～39wt.%; The inhibitor of (3) 0.01～0.05wt.%; The crosslinking agent of (4) 1～3wt.%; The catalyst of (5) 0.1～0.2wt.%.As the raw material of the base glue of insulation adhesion coating, forming is the forming of silicon rubber matrix, inhibitor, crosslinking agent and catalyst containing vinyldimethicone of the end-blocking in the conductive silicon rubber composite, and its quality compositing range is also identical with the compositing range of silicon rubber matrix, inhibitor, crosslinking agent and the catalyst containing vinyldimethicone of end-blocking in the conductive silicon rubber composite.
Concrete each electromagnetic shielding structural conductive silicon rubber, the conductive silicon rubber composite of its bilayer or sandwich construction is identical or different all can.
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 structural conductive silicon rubber for electromagnetic shielding provided by the present invention, is characterized in that, comprises the following steps:
(1) add the rubber matrix containing vinyldimethicone according to above-mentioned formula in mixer or rubber mixing machine, at 25～35 ℃ of temperature, add inhibitor to stir 10～60 minutes, add successively subsequently crosslinking agent, catalyst respectively under vacuum state continuous stirring within 10～30 minutes, make base glue, vacuumize and guarantee and atm difference >=0.09MPa;
(2) putting into base glue and the packing material that step (1) makes in mixer or rubber mixing machine first stirs 10～30 minutes, stir under vacuum state again and within 10～30 minutes, make the conductive silicon rubber mixture, stir environment temperature and be controlled in 15～35 ℃ of scopes in this process, vacuumize and guarantee and atm difference >=0.09MPa;
(3) conductive silicon rubber mixture step (2) made is sulfided into film by the method for extrusion modling, and curing temperature can be selected according to execution conditions in 150～200 ℃ of scopes, cure time 3～10min, sulfide stress 1～30MPa;
(4) will make two or multi-disc thickness and packing material can carry out bonding compound by identical conductive silicon rubber sheet material that can be different according to step (3), be positioned in the extrusion molding dies of desired thickness, between adjacent two lamella conductive silicon rubber sheets, add abundant step (1) to make base glue, place 10～60s and extrude unnecessary insulating cement under the sulfide stress of 1～30MPa, recover subsequently normal pressure and place 1 at 80～130 ℃ of temperature
10min, take out.
Inhibitor in above-mentioned steps (1) is preferably the acetylene cyclohexanol.
Crosslinking agent in above-mentioned steps (1) is preferably linear methylhydrogenpolysi,oxane, containing vinyldimethicone viscosity (25 ℃), is 1000～20000mPas, hydrogen matrix amount content 0.4-0.8%.
Catalyst in above-mentioned steps (1) is preferably the Ka Ersite platinum catalyst, platinum content 3000-5000ppm.
Packing material in above-mentioned steps (2) can be one or more in cladded type conductive filler (as Al contained Ni of nickel content 40～80wt.% nickel coated graphite powder, nickel content 20～60wt.% etc.), monometallic powder or alloy powder (as particle diameter is 1～200 μ m nickel powder, FeNi powders etc.).
Inventive principle
For the conductive silicon rubber that is applied in wide frequency range, it all will have good shielding properties at high frequency, medium and low frequency elect magnetic field.In high-frequency range, mostly conductive silicon rubber is to realize shielding action by excellent electric conductivity.The more intensive complexity of the conductive network of conductive silicon rubber, electric conductivity is better, and the eddy-current loss produced at elect magnetic field is larger, and shielding properties is better.Theoretical and the tunnel-effect theory according to conductive channel, the grain spacing of conductive silicon rubber is the key factor that determines conductive network density.At present, that mostly composite is is fibrous by adding, sheet, dendritic fillers shorten grain spacing, but the filler pattern is more complicated, and mobility when it mixes with matrix is poorer, cause mix inhomogeneous.But from sulfuration process, adopt the curing temperature of 150～200 ℃ can improve the material crosslink density, matrix network is shunk, thereby shorten grain spacing, the conductive path quantity that increase forms because tunnel-effect occurs, and then in the situation that identical filler loading has improved electric conductivity.
But when electromagnetic field frequency reduces, eddy current effect also weakens thereupon, and this has just reduced the shielding action caused by eddy-current loss.Therefore, for the medium and low frequency shielding electromagnetic waves, except setting about from the material aspect, also can increase loss from material structure, improve shield effectiveness.According to S.A.Schelkunoff electromagnetic shielding theory, electromagnet shield effect can be regarded the electromagnetic wave loss sum of three kinds of different mechanism, i.e. absorption loss, reflection loss and multipath reflection loss as.Absorption loss occurs in shield, is dipole and the caused loss of electromagnetic field effect in shielding material, and eddy-current loss is exactly the result of electric dipole and electromagnetic field effect in filler; The multipath reflection loss refers to wears from the shield surface when electromagnetic wave while being mapped to another surface, and the part electromagnetic wave energy can be reflected back in shield, and the loss caused at the shielding intrabed multiples, generally when absorption loss is greater than 10dB, can ignore; And reflection loss is because the wave impedance on air and shield surface is not mated caused.Electromagnetic wave is in communication process, if the impedance of propagation medium changes, electromagnetic wave will reflect at the variation interface.Utilize this characteristic, conductive silicon rubber is made to bilayer or sandwich construction and interlayer increases the insulation glue-line, make in the conductive silicon rubber system to occur twice or impedance variations repeatedly.When Electromagnetic Wave Propagation, in material the time, at interlayer, reflect.With the conductive silicon rubber of non-structure design, compare, structural material has also increased the one or many reflection loss when having identical eddy-current loss, and this has just improved total shielding properties of material.
By adopting structural conductive silicon rubber that technique of the present invention prepares when guaranteeing the General Mechanics performance requirement, can effectively improve shield effectiveness and stability thereof in 100KHz-18GHz wide-band scope.
This material has following characteristics: (1) has saved the filler loading by the adjustment of sulfuration process, saves production cost; (2) when under guaranteeing high frequency, thering is the good electrical magnetic shield performance, improve the shielding properties of medium and low frequency scope, can meet the requirement that all there is good shield effectiveness in wide frequency range; (3) preparation technology is simple.The composite of this patent only comprises sulfuration and the bonding compound three large steps of the mixing of matrix and filler, every layer of conductive silicon rubber, and without filler is carried out to pretreatment, it is single that interlayer connects technique, enhances productivity; (4) can meet the capability of electromagnetic shielding requirement, possess again mechanical property preferably.
The specific embodiment
The embodiment that the present invention exemplifies is only as explanation use of the present invention, and protection of the present invention is described and is as the criterion with claims.
Embodiment 1:
Filler: preferred nickel coated graphite powder (Ni-C), nickel content 40～80wt.%.
At first, add respectively acetylene cyclohexanol inhibitor 0.3g, methylhydrogenpolysi,oxane crosslinking agent 25g, Ka Ersite platinum catalyst 2.0g at 600g containing in the rubber matrix of ethenyl blocking dimethyl silicone polymer, stir and make base glue in 20 minutes at 25～35 ℃ of temperature, vacuumize assurance pressure reduction >=0.09MPa.Secondly, add 1078g nickel coated graphite powder (63.2wt.%), first stir 5 minutes under normal pressure, then stir under vacuum environment 5 minutes again, whipping temp is room temperature, vacuumizes assurance pressure reduction >=0.09MPa.Then, adopt 185 ℃ of curing temperatures that conductive silicon rubber is sulfided into to the print that 1mm is thick.Finally, two thick samples of 1mm are stacked in the extrusion molding dies that 2mm is thick, interlayer adds base glue.Place 10s and extrude unnecessary base glue under the sulfide stress of 10MPa, recover subsequently normal pressure and vulcanize 3min at 125 ℃ of temperature, take out.
Embodiment 2:
Filler: preferred nickel coated graphite powder (Ni-C), nickel content 40～80wt.%.
At first, add respectively acetylene cyclohexanol inhibitor 0.3g, methylhydrogenpolysi,oxane crosslinking agent 25g, Ka Ersite platinum catalyst 2.0g at 600g containing in the rubber matrix of ethenyl blocking dimethyl silicone polymer, stir and make base glue in 20 minutes at 25～35 ℃ of temperature, vacuumize assurance pressure reduction >=0.09MPa.Secondly, add 940g nickel coated graphite powder (60.0wt.%), first stir 5 minutes under normal pressure, then stir under vacuum environment 5 minutes again, whipping temp is room temperature, vacuumizes assurance pressure reduction >=0.09MPa.Then, adopt 185 ℃ of curing temperatures that conductive silicon rubber is sulfided into to the print that 0.9～1mm is thick.Finally, four thick samples of 0.9～1mm are stacked in the extrusion molding dies that 4mm is thick, interlayer adds base glue.Place 10s and extrude unnecessary base glue under the sulfide stress of 10MPa, recover subsequently normal pressure and vulcanize 3min at 125 ℃ of temperature, take out.
Embodiment 3:
Filler: preferred nickel coated graphite powder (Ni-C), nickel content 40～80wt.%.
At first, add respectively acetylene cyclohexanol inhibitor 0.3g, methylhydrogenpolysi,oxane crosslinking agent 25g, Ka Ersite platinum catalyst 4.0g at 700g containing in the rubber matrix of ethenyl blocking dimethyl silicone polymer, stir and make base glue in 20 minutes at 25～35 ℃ of temperature, vacuumize assurance pressure reduction >=0.09MPa.Secondly, add 1296g nickel coated graphite powder (63.9wt.%), first stir 5 minutes under normal pressure, then stir under vacuum environment 5 minutes again, whipping temp is room temperature, vacuumizes assurance pressure reduction >=0.09MPa.Then, adopt 185 ℃ of curing temperatures that conductive silicon rubber is sulfided into to the thick and thick print of a slice 2mm of two 0.5mm.Finally, three samples are stacked in the extrusion molding dies that 3mm is thick, interlayer adds base glue.Place 10s and extrude unnecessary base glue under the sulfide stress of 10MPa, recover subsequently normal pressure and vulcanize 3min at 125 ℃ of temperature, take out.
Embodiment 4:
Filler: preferred Al contained Ni (Ni-Al), nickel content 20～60wt.%.
At first, add respectively acetylene cyclohexanol inhibitor 0.45g, methylhydrogenpolysi,oxane crosslinking agent 25g, Ka Ersite platinum catalyst 3.0g at 600g containing in the rubber matrix of ethenyl blocking dimethyl silicone polymer, stir and make base glue in 60 minutes at 25～35 ℃ of temperature, vacuumize assurance pressure reduction >=0.09MPa.Secondly, add 956g Al contained Ni (60.3wt.%), first stir 5 minutes under normal pressure, then stir under vacuum environment 10 minutes again, whipping temp is room temperature, vacuumizes assurance pressure reduction >=0.09MPa.Then, adopt 160 ℃ of curing temperatures that conductive silicon rubber is sulfided into to the print that 0.9～1mm is thick.Finally, two thick samples of 0.9～1mm are stacked in the extrusion molding dies that 2mm is thick, interlayer adds base glue.Place 20s and extrude unnecessary base glue under the sulfide stress of 10MPa, recover subsequently normal pressure and vulcanize 10min at 80 ℃ of temperature, take out.
Embodiment 5:
Filler: preferred Al contained Ni (Ni-Al), nickel content 20～60wt.%.
At first, add respectively acetylene cyclohexanol inhibitor 0.45g, methylhydrogenpolysi,oxane crosslinking agent 25g, Ka Ersite platinum catalyst 3.0g at 600g containing in the rubber matrix of ethenyl blocking dimethyl silicone polymer, stir and make base glue in 60 minutes at 25～35 ℃ of temperature, vacuumize assurance pressure reduction >=0.09MPa.Secondly, add 1029g Al contained Ni (62.1wt.%), first stir 5 minutes under normal pressure, then stir under vacuum environment 10 minutes again, whipping temp is room temperature, vacuumizes assurance pressure reduction >=0.09MPa.Then, adopt 160 ℃ of curing temperatures that conductive silicon rubber is sulfided into to the print that 2mm is thick.Finally, two thick samples of 2mm are stacked in the extrusion molding dies that 4mm is thick, interlayer adds base glue.Place 20s and extrude unnecessary base glue under the sulfide stress of 10MPa, recover subsequently normal pressure and vulcanize 10min at 80 ℃ of temperature, take out.
Embodiment 6:
Filler: nickel powder (Ni).
At first, add respectively acetylene cyclohexanol inhibitor 0.5g, methylhydrogenpolysi,oxane crosslinking agent 40g, Ka Ersite platinum catalyst 3.5g at 600g containing in the rubber matrix of ethenyl blocking dimethyl silicone polymer, stir and make base glue in 45 minutes at 25～35 ℃ of temperature, vacuumize assurance pressure reduction >=0.09MPa.Secondly, add 1030g nickel powder (61.5wt.%), first stir 10 minutes under normal pressure, then stir under vacuum environment 20 minutes again, whipping temp is room temperature, vacuumizes assurance pressure reduction >=0.09MPa.Then, adopt 200 ℃ of curing temperatures that conductive silicon rubber is sulfided into to the print that 1mm is thick.Finally, two thick samples of 1mm are stacked in the extrusion molding dies that 2mm is thick, interlayer adds base glue.Place 10s and extrude unnecessary base glue under the sulfide stress of 10MPa, recover subsequently normal pressure and vulcanize 10min at 100 ℃ of temperature, take out.
Embodiment 7:
Filler: nickel powder (Ni).
At first, add respectively acetylene cyclohexanol inhibitor 0.5g, methylhydrogenpolysi,oxane crosslinking agent 40g, Ka Ersite platinum catalyst 3.5g at 600g containing in the rubber matrix of ethenyl blocking dimethyl silicone polymer, stir and make base glue in 45 minutes at 25～35 ℃ of temperature, vacuumize assurance pressure reduction >=0.09MPa.Secondly, add 1056g nickel powder (62.1wt.%), first stir 10 minutes under normal pressure, then stir under vacuum environment 20 minutes again, whipping temp is room temperature, vacuumizes assurance pressure reduction >=0.09MPa.Then, adopt 200 ℃ of curing temperatures that conductive silicon rubber is sulfided into to the print that 1mm is thick.Finally, three thick samples of 1mm are stacked in the extrusion molding dies that 3mm is thick, interlayer adds base glue.Place 10s and extrude unnecessary base glue under the sulfide stress of 10MPa, recover subsequently normal pressure and vulcanize 10min at 100 ℃ of temperature, take out.
Comparative Examples 1:
With embodiment 1, contrasted, filler is preferred nickel coated graphite powder (Ni-C), nickel content 40～80wt.%.
At first, add respectively acetylene cyclohexanol inhibitor 0.3g, methylhydrogenpolysi,oxane crosslinking agent 25g, Ka Ersite platinum catalyst 2.0g at 600g containing in the rubber matrix of ethenyl blocking dimethyl silicone polymer, stir and make base glue in 20 minutes at 25～35 ℃ of temperature, vacuumize assurance pressure reduction >=0.09MPa.Secondly, add 1078g nickel coated graphite powder (63.2wt.%), first stir 5 minutes under normal pressure, then stir under vacuum environment 5 minutes again, whipping temp is room temperature, vacuumizes assurance pressure reduction >=0.09MPa.Finally, conductive silicon rubber is placed in to the 2mm mould, adopts 185 ℃ of curing temperatures that mixture is sulfided into to the print that 2mm is thick, take out.
Comparative Examples 2:
With embodiment 1, contrasted, filler is preferred nickel coated graphite powder (Ni-C), the thick individual layer sample of the 2mm made according to patent CN102276988A step.
Comparative Examples 3:
With embodiment 4(bilayer) contrasted.Filler is preferred Al contained Ni (Ni-Al), nickel content 20～60wt.%.
At first, add respectively acetylene cyclohexanol inhibitor 0.45g, methylhydrogenpolysi,oxane crosslinking agent 25g, Ka Ersite platinum catalyst 3.0g at 600g containing in the rubber matrix of ethenyl blocking dimethyl silicone polymer, stir and make base glue in 60 minutes at 25～35 ℃ of temperature, vacuumize assurance pressure reduction >=0.09MPa.Secondly, add 956g Al contained Ni (60.3wt.%), first stir 5 minutes under normal pressure, then stir under vacuum environment 10 minutes again, whipping temp is room temperature, vacuumizes assurance pressure reduction >=0.09MPa.Finally, conductive silicon rubber is placed in to the 2mm mould, adopts 185 ℃ of curing temperatures that mixture is sulfided into to the print that 2mm is thick, take out.
Comparative Examples 4:
With embodiment 6, contrasted, filler is nickel powder (Ni).
At first, add respectively acetylene cyclohexanol inhibitor 0.5g, methylhydrogenpolysi,oxane crosslinking agent 40g, Ka Ersite platinum catalyst 3.5g at 600g containing in the rubber matrix of ethenyl blocking dimethyl silicone polymer, stir and make base glue in 45 minutes at 25～35 ℃ of temperature, vacuumize assurance pressure reduction >=0.09MPa.Secondly, add 1030g nickel powder (61.5wt.%), first stir 10 minutes under normal pressure, then stir under vacuum environment 20 minutes again, whipping temp is room temperature, vacuumizes assurance pressure reduction >=0.09MPa.Finally, conductive silicon rubber is placed in to the 2mm mould, adopts 200 ℃ of curing temperatures that mixture is sulfided into to the print that 2mm is thick, take out.
Experimental data:
The index parameter that following table is conductive rubber composite material.
From the table data known, identical at filling kind, but filler loading and formula be all in different situation, containing embodiment 1 sample of 63wt.% filler under 100KHz～100MHz frequency range than the high 6～17dB of patent sample (Comparative Examples 2) containing the 67wt.% filler.
In addition, in the situation that composite-material formula is identical, embodiment 1 sample under 20MHz～2GHz frequency range shield effectiveness than the high 18～31dB of Comparative Examples 1 sample; The shield effectiveness of embodiment 4 samples under 100KHz～18GHz frequency range is than the high 10～30dB of Comparative Examples 3 sample; The shield effectiveness of embodiment 6 samples under 100KHz～100MHz frequency range is than the Comparative Examples high 10dB of 4 sample left and right.Therefore, the sample that carries out structural design can effectively improve the capability of electromagnetic shielding of composite, especially works as wave frequency and is less than in the medium and low frequency situation of 2GHz, and its electromagnet shield effect is apparently higher than the individual layer conductive rubber composite material.
Claims (9)
1. electromagnetic shielding structural conductive silicon rubber, it is characterized in that, this material adopts the conductive silicon rubber composite of bilayer or sandwich construction, and be coated with one deck base glue as the insulation adhesion coating at interlayer, form " sandwich " structure, the raw material of its conductive silicon rubber composite forms: the packing material of (1) 59～64wt.%, the silicon rubber matrix containing vinyldimethicone of the end-blocking of (2) 34～39wt.%; The inhibitor of (3) 0.01～0.05wt.%; The crosslinking agent of (4) 1～3wt.%; The catalyst of (5) 0.1～0.2wt.%; As the raw material of the base glue of insulation adhesion coating, forming is the forming of silicon rubber matrix, inhibitor, crosslinking agent and catalyst containing vinyldimethicone of the end-blocking in the conductive silicon rubber composite, and its quality compositing range is also identical with the compositing range of silicon rubber matrix, inhibitor, crosslinking agent and the catalyst containing vinyldimethicone of end-blocking in the conductive silicon rubber composite;
Packing material in above-mentioned steps (2) is one or more in cladded type conductive filler, monometallic powder or alloy powder.
2. according to the electromagnetic shielding of claim 1 structural conductive silicon rubber, it is characterized in that, each electromagnetic shielding structural conductive silicon rubber, the conductive silicon rubber composite of its bilayer or sandwich construction is identical or different all can.
3. according to the electromagnetic shielding of claim 1 structural conductive silicon rubber, it is characterized in that, the thickness of every layer of conductive silicon rubber composite is 0.5～4mm.
4. according to the electromagnetic shielding of claim 1 structural conductive silicon rubber, it is characterized in that the thickness≤0.1mm of insulation adhesion coating.
5. according to the electromagnetic shielding of claim 1 structural conductive silicon rubber, it is characterized in that, the inhibitor in step (1) is preferably the acetylene cyclohexanol.
6. according to the electromagnetic shielding of claim 1 structural conductive silicon rubber, it is characterized in that, crosslinking agent in step (1) is preferably linear methylhydrogenpolysi,oxane, containing 25 ℃ of viscositys of vinyldimethicone, is 1000～20000mPas, hydrogen matrix amount content 0.4-0.8%.
7. according to the electromagnetic shielding of claim 1 structural conductive silicon rubber, it is characterized in that, the catalyst in step (1) is preferably the Ka Ersite platinum catalyst, platinum content 3000-5000ppm.
8. according to arbitrary electromagnetic shielding structural conductive silicon rubber of claim 1-7, it is characterized in that one or more in Al contained Ni, nickel powder or FeNi powders that packing material is nickel content 40～80wt.% nickel coated graphite powder, nickel content 20～60wt.%.
9. prepare the method for the described arbitrary electromagnetic shielding of claim 1-7 with structural conductive silicon rubber, it is characterized in that, comprise the following steps:
(1) add the rubber matrix containing vinyldimethicone according to above-mentioned formula in mixer or rubber mixing machine, at 25～35 ℃ of temperature, add inhibitor to stir 10～60 minutes, add successively subsequently crosslinking agent, catalyst respectively under vacuum state continuous stirring within 10～30 minutes, make base glue, vacuumize and guarantee and atm difference >=0.09MPa;
(2) putting into base glue and the packing material that step (1) makes in mixer or rubber mixing machine first stirs 10～30 minutes, stir under vacuum state again and within 10～30 minutes, make the conductive silicon rubber mixture, stir environment temperature and be controlled in 15～35 ℃ of scopes in this process, vacuumize and guarantee and atm difference >=0.09MPa;
(3) conductive silicon rubber mixture step (2) made is sulfided into film by the method for extrusion modling, and curing temperature can be selected according to execution conditions in 150～200 ℃ of scopes, cure time 3～10min, sulfide stress 1～30MPa;
(4) will make two or multi-disc thickness and packing material can carry out bonding compound by identical conductive silicon rubber sheet material that can be different according to step (3), be positioned in the extrusion molding dies of desired thickness, between adjacent two lamella conductive silicon rubber sheets, add abundant step (1) to make base glue, place 10～60s and extrude unnecessary insulating cement under the sulfide stress of 1～30MPa, recover subsequently normal pressure and place 1～10min at 80～130 ℃ of temperature, take out.
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| CN111560125A (en) * | 2020-05-25 | 2020-08-21 | 惠州市海鸿水泥制品有限公司 | Conductive composite material and preparation method thereof |
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