CN106413367B - A kind of multifunctional macromolecule Quito layer electromagnetic shielding material and preparation method thereof - Google Patents
A kind of multifunctional macromolecule Quito layer electromagnetic shielding material and preparation method thereof Download PDFInfo
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- CN106413367B CN106413367B CN201610801400.1A CN201610801400A CN106413367B CN 106413367 B CN106413367 B CN 106413367B CN 201610801400 A CN201610801400 A CN 201610801400A CN 106413367 B CN106413367 B CN 106413367B
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- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K9/00—Screening of apparatus or components against electric or magnetic fields
- H05K9/0073—Shielding materials
- H05K9/0081—Electromagnetic shielding materials, e.g. EMI, RFI shielding
- H05K9/0088—Electromagnetic shielding materials, e.g. EMI, RFI shielding comprising a plurality of shielding layers; combining different shielding material structure
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
- B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
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- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
- B32B27/20—Layered products comprising a layer of synthetic resin characterised by the use of special additives using fillers, pigments, thixotroping agents
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2250/00—Layers arrangement
- B32B2250/24—All layers being polymeric
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2262/00—Composition or structural features of fibres which form a fibrous or filamentary layer or are present as additives
- B32B2262/10—Inorganic fibres
- B32B2262/106—Carbon fibres, e.g. graphite fibres
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2264/00—Composition or properties of particles which form a particulate layer or are present as additives
- B32B2264/10—Inorganic particles
- B32B2264/105—Metal
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2264/00—Composition or properties of particles which form a particulate layer or are present as additives
- B32B2264/10—Inorganic particles
- B32B2264/107—Ceramic
- B32B2264/108—Carbon, e.g. graphite particles
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2307/00—Properties of the layers or laminate
- B32B2307/20—Properties of the layers or laminate having particular electrical or magnetic properties, e.g. piezoelectric
- B32B2307/212—Electromagnetic interference shielding
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Abstract
The invention discloses a kind of multifunctional macromolecule Quito layer electromagnetic shielding materials and preparation method thereof, and material made from this method is made of conductive functional layers and complex functional layer, and is extruded into the multilayered structure that two-phase is arranged alternately by multilayer extrusion system melt.Wherein, conductive functional layers are the polymer-based conducing composite materials of conducting particles filling, and complex functional layer is the particle-filled polymer-based composite of complex function, and the complex function particle is mixed by conducting particles and other functional particles.There are a large amount of layered interfaces in the material, and are being parallel to bed boundary direction and are all having electric conductivity perpendicular to bed boundary direction.The number of plies, thickness of alternate multiple material obtained by preparation method provided by the invention, layer structure and performance are controllable, and composition of raw materials is adjustable；Electromagnetic shielding performance and other complex functions are excellent；Required raw material be it is commercially available, it is at low cost；Preparation method is simple, high production efficiency and can be produced with continuous batch.
Description
Technical field
The invention belongs to polymer matrix functional composite material preparation process fields, and in particular to a kind of multifunctional macromolecule base
Multilayer electromagnetic shielding material and preparation method thereof.
Background technique
With the development with microelectronic device, wireless transmission etc. for the modern science and technology of representative, electromagnetic wave is in the life for the mankind
Generate it is living while provide convenient, increasingly become influence human health, information security, equipment stablizes it is very important " stealthy
Killer ".Electromagnetic radiation has become the another serious pollution after atmosphere pollution, water pollution.It the use of shielding material is a kind of letter
It is single, the effective method for inhibiting electromagnetic radiation.Compared with metal material, the polymer matrix electromagnetic shielding material of conducting particles filling
The advantages that light, plastic, anti-corrosion because of its, is gradually applied to the fields such as electric, instrument communication, defense military.But with
Every profession and trade to material thin wall, lightweight requirements it is growing day by day, more harsh challenge is proposed to its electromagnetic shielding performance.
At the same time, with the development of society, the material of simple function has been difficult to meet the needs of people, the multifunction gesture of material
The trend of social development must be become.It, will if making it have the multiple functions such as fire-retardant on the basis of with electro-magnetic screen function
It is greatly improved in the application in protective materials field.Therefore, how to design preparation has electromagnetic shielding performance and excellent flame etc.
Multifunctional polymer based composites have important theory and realistic meaning.
For the polymer matrix electromagnetic shielding material of conducting particles filling, the key that obtain excellent electromagnetic shielding properties exists
Construct perfect conductive network in how to improve the dispersion of conducting particles in a polymer matrix, thus increase composite material with
The thermal losses generated during the resistance difference and electromagnetic conversion of external agency in material internal.It realizes multifunction, needs
It is compound to add the progress of other function particle, and traditional blend method is difficult to realize the synergistic of conducting particles Yu other function particle
It is compound.Therefore, how in a polymer matrix the key problem for high-efficiency multi-function being realized under low conducting particles loading is
It constructs with the multi-functional composite network of synergistic effect.
Compared to single-layer shield structural material, multilayer screen structural material material select and in terms of have
Bigger design space.By reasonable optimization design, more bed boundarys are introduced, conducting particles divides in limited space
It dissipates, forms fine and close conductive network, make electromagnetic wave in material internal through multiple reflections, to obtain better shield effectiveness.With
This designs the multilayered structure that conductive functional layers and complex functional layer are arranged alternately, may be easy to regulation conducting particles and its simultaneously
The dispersion of his functional particles greatly improves the comprehensive performance of material to construct compound multifunctional network.
Summary of the invention
The purpose of the present invention is the preparation present situations of the polymer matrix electromagnetic shielding material for conducting particles filling, and provide
A kind of preparation method of multifunctional macromolecule Quito layer electromagnetic shielding material, i.e. polymer-matrix electric conduction functional layer and polymer matrix are multiple
The multilayer screen material that is arranged alternately of functional layer is closed, existing electromagnetic shielding material shield effectiveness is poor, morphosis is difficult to solve
The problems such as designing, having a single function.
The technical scheme is that by the object of the material of polymer-based conductive functional layers and polymer-based complex functional layer
Material is squeezed out through extruder fusion plastification respectively, and after junction station exit is superimposed together and to form following initial configuration, then is passed through
The multiple stratiform overlapping effect for the several layers multiplier connecting with the junction station is crossed, there is two-phase to be arranged alternately multilayer for formation
The extrudate of structure, i.e., polymer-based multilayer materials:
(1) material of the polymer-based conductive functional layers is multiple by the particle-filled polymer-based conduction of conducting function
Condensation material；
(2) material of the polymer-based complex functional layer is multiple by the particle-filled polymer-based conduction of complex function
Condensation material, in which: the complex function particle is mixed by conducting function particle and other functional particles；
(3) initial configuration can be by polymer-based conductive functional layers and polymer-based complex functional layer overlapping and
At two-layer structure, or by polymer-based conductive functional layers, polymer-based complex functional layer, polymer-based conductive functional layers
The three-decker being successively formed by stacking, or by polymer-based complex functional layer, polymer-based conductive functional layers, polymer-based
The three-decker that complex functional layer is successively formed by stacking；
In the above-mentioned technical solutions, the macromolecule matrix in the polymer-based multilayer electromagnetic shielding material is selected from poly- second
Alkene, polyvinyl chloride, polymethyl methacrylate, polystyrene, Kynoar, polyamide, polyester, polyformaldehyde, gathers polypropylene
Urethane, styrene analog thermoplastic elastomer, polyester-type thermoplastic elastomer, polyolefins thermoplastic elastomer, polyacrylate
One of analog thermoplastic elastomer, EP rubbers, butadiene-styrene rubber, neoprene, silicon rubber, fluorubber, natural rubber are more
Kind；Wherein, the macromolecule matrix in the polymer-based conductive functional layers and the polymer-based complex functional layer is selected from upper
It states same or not of the same race in material.
In the above-mentioned technical solutions, the conducting function particle in the polymer-based conductive functional layers is metal, carbon black, carbon
One of nanotube, graphene, carbon fiber are a variety of, mass fraction 0.01-60%.
In the above-mentioned technical solutions, the conducting function particle in the polymer-based complex functional layer is metal, carbon black, carbon
One of nanotube, graphene, carbon fiber are a variety of, and other functional particles are the ball for not including above-mentioned conducting function particle
One of shape, threadiness, sheet, different form inorganic particulate or organic filler are a variety of；The polymer-based complex functional layer
The mass fraction of middle complex function particle is 0.01-60%, and the mass fraction of conducting function particle is in complex function particle
0.01-99.9%。
In the above-mentioned technical solutions, the polymer-based multilayer electromagnetic shielding material is being parallel to bed boundary direction and vertical
Electric conductivity is all had in bed boundary direction, and conductivity, electromagnetic shielding performance and other complex functions can pass through function grain
Sub- content, Thickness ratio, the number of plies, functional particles partial size, alternately one of initial configuration of stratified material or various ways carry out
Regulation.
In the above-mentioned technical solutions, the extrudate is by two extruders (A, B), junction station (C), several layers multiplier
(D), the multilayer extrusion system of outlet mold (E) and cooling tractor (F) composition is prepared by melting extrusion, and performance can
By the thickness ratio of the overall thickness of the extrudate, total number of plies, polymer-based conductive functional layers and polymer-based complex functional layer,
The loading of functional particles is regulated and controled, in which: the overall thickness of extrudate is 0.01-10mm；Total number of plies number is 2-32769；
The thickness ratio of the polymer-based conductive functional layers and polymer-based complex functional layer is 1:99-99:1.
The number of plies of the extrudate initial configuration can adjust runner number by the switch in the junction station (C)
Control: the initial configuration that the initial configuration that 2 runners obtain is 2 layers, 3 runners obtain is 3 layers.
In the above-mentioned technical solutions, the number of plies of the extrudate can by the initial configuration number of plies and layer multiplier number according to
Following manner is regulated and controled:
(1) when initial configuration is 2 layers, and uses n layer multiplier, the number of plies of extrudate is 2(n+1)Layer, in which: n is
0-14；
(2) when initial configuration is 3 layers, and uses n layer multiplier, the number of plies of extrudate is 2(n+1)+ 1 layer, in which: n
For 0-14.
In the above-mentioned technical solutions, material obtained is film, sheet material, plate, special section, fibre according to the actual application
Dimension.
The present invention has the advantage that the one-pass molding work that 1, preparation method provided by the invention uses lamellar composite to squeeze out
Skill, preparation method is simple, convenient operation and control, high production efficiency；By adjusting the runner number of junction station (C), can adjust
The initial configuration of the whole alternate multiple material is 2 layers or 3 layers；Pass through the extrusion revolving speed of regulation and control two extruders
Than the thickness of adjustable polymer-based conductive functional layers and polymer-based complex functional layer；Pass through the number of control layer multiplier
Amount, total number of plies of the adjustable alternate multiple material.
2, the polymer-based multilayer electromagnetic shielding material prepared through the invention is polymer-based conductive functional layers with it is compound
The multilayered structure that functional layer is arranged alternately, the structure perpendicular to bed boundary direction and are being parallel to bed boundary direction and are all having and leading
Electrically, it can effectively improve the electromagnetic shielding performance of material.
3, the polymer-based multilayer electromagnetic shielding material prepared through the invention is being parallel to bed boundary direction, conducting particles
It is distributed in restricted clearance, fine and close conductive network can be formed.Especially in complex functional layer, due to other function particle
In the presence of the dispersion of conducting particles can not only being induced, but also volume excretion can be played, to reduce conductive excess effusion value, raising
Conductivity, allows the multilayer screen material to realize high electromagnetic shielding performance under low conducting particles content.
4, the polymer-based multilayer electromagnetic shielding material prepared through the invention has multifunctionality, polymer-based conduction function
Ergosphere is arranged alternately with complex functional layer, the dispersion of mutual induction conducting particles and other function particle, and Effective Regulation is conductive-more
Function and service network forms synergistic effect, to obtain high-performance Multifunctional electromagnetic shielding material.
The present invention also has the advantages that more otherwise.
Detailed description of the invention
Fig. 1 is the preparation of layer multiplication extruding technology alternate multiple composite material.A in the figure, B: extruder, C:
Junction station, D: layer multiplier, E: outlet mold, F: traction cooling device, G- squeeze out sample.
Specific embodiment
The present invention is further described specifically by the following examples.In following embodiment, each component
Dosage is quality dosage.It is necessarily pointed out that following embodiment is served only for, the present invention is described further, no
It can be interpreted as limiting the scope of the invention, field person skilled in the art is the present invention according to aforementioned present invention content
Some nonessential modifications and adaptations out, still fall within protection scope of the present invention.
The good effect that the present invention generates can be illustrated with embodiment.
Embodiment 1
(1) raw material be thermoplastic polyurethane (TPU) (58A, BASF), carbon nanotube (CNT), expansion type flame retardant (IFR),
Conductive functional layers are carbon nano-tube filled thermoplastic polyurethane, complex functional layer is carbon nanotube and expansion type flame retardant is compound fills out
Fill thermoplastic polyurethane.It is dried using preceding raw material is placed in 80 DEG C of vacuum drying ovens for 24 hours to remove moisture.Conductive function is prepared first
TPU and the CNT melting mixing in double screw extruder after drying is granulated, temperature 185 by ergosphere and complex functional layer master batch
DEG C, the TPU/CNT compound master batch containing 6wt%CNT is prepared；By the TPU after drying with CNT, IFR in double screw extruder
Middle melting mixing is granulated, and temperature is 185 DEG C, and the TPU/CNT/IFR compound master batch containing 1wt%CNT, 30wt%IFR is prepared；
(2) conductive functional layers and complex functional layer master batch are put into two extruders (A, B) of multilayer extrusion system respectively
In (see figure 1), the rotating ratio 1:1 of extruder is adjusted, extruder temperature of each section is controlled respectively at 175 DEG C -180 DEG C -185 DEG C -185
℃.After material melts plasticizing in extruder, overlap two strands of melts in the junction station C of two runners, obtaining the number of plies is 2 layers
Initial configuration, then flowed out from the outlet mold E of rectangularl runner after the cutting and layering superposition of 6 layer multiplier D, wherein converging
The temperature of device C, layer multiplier D and outlet mold E are 185 DEG C or so, using the compacting of tri-roll press machine and leading for dragger
Draw, thickness 1.6mm can be obtained, conductive functional layers and complex functional layer Thickness ratio are 1:1, and the sheet that the number of plies is 128 layers replaces
Laminar composite.Electric performance test the results show that the material be parallel to bed boundary direction and perpendicular to bed boundary direction it is equal
Conductive, being parallel to bed boundary direction conductivity is 60 S/m, is 26S/m perpendicular to bed boundary direction conductivity;Electromagnetism
Shielding properties test display, X-band masking value reach 55dB, and limit oxygen index test result shows that limit oxygen index reaches
33%。
Comparative example 1
As a comparison, in the master batch preparation of the first step, prepare respectively TPU/CNT compound master batch containing 6wt%CNT and
TPU/CNT/IFR compound master batch containing 1wt%CNT, 20wt%IFR.Second step implementation method is same as Example 1, finally
To with a thickness of 1.6mm, conductive functional layers and complex functional layer Thickness ratio are 1:1, and the sheet that the number of plies is 128 layers replaces lamellar composite
Material.Electric performance test is the results show that the material is being parallel to bed boundary direction and is all having conduction perpendicular to bed boundary direction
Property, being parallel to bed boundary direction conductivity is 50S/m, is 20S/m perpendicular to bed boundary direction conductivity；Electromagnetic shielding performance is surveyed
Examination display, X-band masking value reach 47dB；Limit oxygen index test result shows that limit oxygen index reaches 29%.It can be seen that
The present invention can regulate and control the electricity of the multilayer material by changing the content of functional particles in complex functional layer according to actual needs
Conductance, electromagnetic shielding and flame retardant property.
Embodiment 2
(1) raw material is polypropylene (PP), carbon black (CB), nano montmorillonite (MMT), and conductive functional layers are carbon black filled poly- third
Alkene, complex functional layer are carbon black and the composite filled polypropylene of nano montmorillonite.Raw material is placed in 80 DEG C of vacuum drying ovens using preceding
Drying is for 24 hours to remove moisture.Prepare conductive functional layers and complex functional layer master batch first, by after drying PP and CB in twin-screw
Melting mixing is granulated in extruder, and temperature is 200 DEG C, and the PP/CB compound master batch containing 15wt%CB is prepared；After dry
PP and CB, MMT in double screw extruder melting mixing be granulated, temperature be 200 DEG C, be prepared containing 15wt%CB, 20wt%
The PP/CB/MMT compound master batch of MMT；
(2) conductive functional layers and complex functional layer master batch are put into two extruders (A, B) of multilayer extrusion system respectively
In (see figure 1), the rotating ratio 1:3 of extruder is adjusted, extruder temperature of each section is controlled respectively at 185 DEG C -190 DEG C -200 DEG C -200
℃.After material melts plasticizing in extruder, overlap two strands of melts in the junction station C of three runners, obtaining the number of plies is 3 layers
Initial configuration, then flowed out from the outlet mold E of rectangularl runner after the cutting and layering superposition of 8 layer multiplier D, wherein converging
The temperature of device C, layer multiplier D and outlet mold E are 200 DEG C or so, using the compacting of tri-roll press machine and leading for dragger
Draw, can be obtained with a thickness of 1.6mm, conductive functional layers and complex functional layer Thickness ratio are 1:3, and the sheet that the number of plies is 513 layers is handed over
For laminar composite.Electric performance test is the results show that the material is being parallel to bed boundary direction and perpendicular to bed boundary direction
Electric conductivity is all had, being parallel to bed boundary direction conductivity is 10S/m, is 5 S/m perpendicular to bed boundary direction conductivity；;Electricity
Magnetic shield performance test display, X-band masking value reach 35dB；Barrier property test result shows, O2Infiltration coefficient can reach
4.205*10-15cm3·cm/cm2·s·Pa。
Comparative example 2
As a comparison, in second step, the rotating ratio of conductive functional layers and complex functional layer is adjusted to 3:1, other are the same as real
Apply example 2.It is computed, material overall thickness is 1.6mm, and the thickness ratio of conductive functional layers and complex functional layer is 3:1, and total number of plies is
513 layers.Electric performance test is the results show that the material is being parallel to bed boundary direction and is all having conduction perpendicular to bed boundary direction
Property, being parallel to bed boundary direction conductivity is 6 S/m, is 2 S/m perpendicular to bed boundary direction conductivity;Electromagnetic shielding performance is surveyed
Examination display, X-band masking value reach 30dB；Barrier property test result shows, O2Infiltration coefficient is 8.215*10-15cm3·cm/
cm2·s·Pa.It can be seen that the present invention can according to actual needs, by the layer for changing complex functional layer and conductive functional layers
Thickness rate regulates and controls conductivity, electromagnetic shielding and the barrier property of the multilayer material.
Embodiment 3
(1) raw material is polyethylene (PE), graphene (Gr), expansion type flame retardant (IFR), and conductive functional layers are filled out for graphene
Fill polyethylene, complex functional layer is graphene and the composite filled polyethylene of expansion type flame retardant.Raw material is placed in 80 DEG C using preceding
It dries in vacuum drying oven for 24 hours to remove moisture.Prepare conductive functional layers and complex functional layer master batch first, by after drying PE with
Gr melting mixing in double screw extruder is granulated, and temperature is 200 DEG C, and the PE/Gr compound master batch containing 4wt%Gr is prepared；
PE and Gr, IFR melting mixing in double screw extruder after drying is granulated, temperature is 200 DEG C, is prepared containing 4wt%
The PE/Gr/IFR compound master batch of Gr, 20wt%IFR；
(2) conductive functional layers and complex functional layer master batch are put into two extruders (A, B) of multilayer extrusion system respectively
In (see figure 1), the rotating ratio 1:1 of extruder is adjusted, extruder temperature of each section is controlled respectively at 170 DEG C -185 DEG C -200 DEG C -200
℃.After material melts plasticizing in extruder, overlap two strands of melts in the junction station C of three runners, obtaining the number of plies is 3 layers
Initial configuration, then flowed out from the outlet mold E of rectangularl runner after the cutting and layering superposition of 9 layer multiplier D, wherein converging
The temperature of device C, layer multiplier D and outlet mold E are 200 DEG C or so, using the compacting of tri-roll press machine and leading for dragger
Draw, can be obtained with a thickness of 1.6mm, conductive functional layers and complex functional layer Thickness ratio are 1:1, and the sheet that the number of plies is 1025 layers is handed over
For laminar composite.Electric performance test is the results show that the material is being parallel to bed boundary direction and perpendicular to bed boundary direction
Electric conductivity is all had, being parallel to bed boundary direction conductivity is 55 S/m, is 25 S/m perpendicular to bed boundary direction conductivity;
Electromagnetic shielding performance test display, X-band masking value reach 45dB；Limit oxygen index test result shows that limit oxygen index reaches
To 30%.
Comparative example 3
As a comparison, in second step, the number of multiplier is changed to 3, other are the same as embodiment 3.Obtain with a thickness of
1.6mm, conductive functional layers replace laminar composite than the sheet for being 17 layers for 1:1, the number of plies with the thickness of complex functional layer.Electricity
The performance test results show that the material is being parallel to bed boundary direction and is all having electric conductivity perpendicular to bed boundary direction, in parallel
It is 50 S/m in bed boundary direction conductivity, is 20S/m perpendicular to bed boundary direction conductivity;Electromagnetic shielding performance test is aobvious
Show, X-band masking value reaches 35dB；Limit oxygen index test result shows that limit oxygen index reaches 27%.It can be seen that this hair
It is bright to regulate and control conductivity, electromagnetic shielding and the resistance of the multilayer material by changing the multilayer material number of plies according to actual needs
Fire performance.
Embodiment 4
(1) raw material is polyolefin elastomer (POE), copper powder (Cu), hollow glass micropearl (HGB, 60 μm of partial size), conductive function
Ergosphere is copper powder filled polyolefin elastomer, complex functional layer is copper powder and hollow glass micropearl with sound insulation effect is compound fills out
Fill polyolefin elastomer.It is dried using preceding raw material is placed in 80 DEG C of vacuum drying ovens for 24 hours to remove moisture.Conductive function is prepared first
POE and the Cu melting mixing in double screw extruder after drying is granulated, temperature 190 by ergosphere and complex functional layer master batch
DEG C, the POE/Cu compound master batch of the Cu containing 20wt% is prepared；By the POE after drying with Cu, HGB in double screw extruder
Melting mixing is granulated, and temperature is 190 DEG C, and the POE/Cu/ HGB compound master batch containing 10wt%Cu, 15wt% HGB is prepared；
(2) conductive functional layers and complex functional layer master batch are put into two extruders (A, B) of multilayer extrusion system respectively
In (see figure 1), the rotating ratio 1:1 of extruder is adjusted, extruder temperature of each section is controlled respectively at 115 DEG C -170 DEG C -185 DEG C -190
℃.After material melts plasticizing in extruder, overlap two strands of melts in the junction station C of three runners, obtaining the number of plies is 3 layers
Initial configuration, then flowed out from the outlet mold E of rectangularl runner after the cutting and layering superposition of 7 layer multiplier D, wherein converging
The temperature of device C, layer multiplier D and outlet mold E are 190 DEG C or so, using the compacting of tri-roll press machine and leading for dragger
Draw, can be obtained with a thickness of 1.6mm, conductive functional layers and complex functional layer Thickness ratio are 1:1, and the sheet that the number of plies is 257 layers is handed over
For laminar composite.Electric performance test is the results show that the material is being parallel to bed boundary direction and perpendicular to bed boundary direction
Electric conductivity is all had, being parallel to bed boundary direction conductivity is 20 S/m;It is 14 S/m perpendicular to bed boundary direction conductivity;
Electromagnetic shielding performance test display, X-band masking value reach 35dB；The performance test results such as sound insulation are shown, in 100-2500Hz
The mean transmission loss of third-octave can reach 25dB.
Comparative example 4
As a comparison, the hollow glass micropearl partial size selected in embodiment 4 is become 20 μm, other are with embodiment 4, finally
It obtains with a thickness of 1.6mm, conductive functional layers and complex functional layer Thickness ratio are 1:1, and it is multiple that the sheet that the number of plies is 257 layers replaces stratiform
Condensation material.Electric performance test is the results show that the material is led being parallel to bed boundary direction and all have perpendicular to bed boundary direction
Electrically, being parallel to bed boundary direction conductivity is 15 S/m;It is 8 S/m perpendicular to bed boundary direction conductivity；Electromagnetic wave shielding
Display can be tested, X-band masking value reaches 28dB；The performance test results such as sound insulation are shown, in the third-octave of 100-2500Hz
Mean transmission loss can reach 23dB.It can be seen that the present invention can according to actual needs, by changing function in complex functional layer
Can the partial size of particle regulate and control conductivity, electromagnetic shielding and the sound insulation property of the multilayer material.
Embodiment 5
(1) raw material is polypropylene (PP), carbon nanotube (CNT), nm-class boron nitride (BN), and conductive functional layers are carbon nanotube
Filled polypropylene, complex functional layer are carbon nanotube and the composite filled polypropylene of nm-class boron nitride.Raw material is placed in 80 using preceding
It dries in DEG C vacuum drying oven for 24 hours to remove moisture.Conductive functional layers and complex functional layer master batch are prepared first, by the PP after drying
Melting mixing is granulated in double screw extruder with CNT, and temperature is 200 DEG C, and the PP/CNT compound containing 6wt%CNT is prepared
Master batch；PP and CNT, BN melting mixing in double screw extruder after drying is granulated, temperature is 200 DEG C, is prepared and contains
The PP/CNT/BN compound master batch of 1wt%CNT, 30wt%BN；
(2) conductive functional layers and complex functional layer master batch are put into two extruders (A, B) of multilayer extrusion system respectively
In (see figure 1), the rotating ratio 1:1 of extruder is adjusted, extruder temperature of each section is controlled respectively at 185 DEG C -190 DEG C -200 DEG C -200
℃.After material melts plasticizing in extruder, overlap two strands of melts in the junction station C of three runners, obtaining the number of plies is 3 layers
Initial configuration, then flowed out from the outlet mold E of rectangularl runner after the cutting and layering superposition of 9 layer multiplier D, wherein converging
The temperature of device C, layer multiplier D and outlet mold E are 200 DEG C or so, using the compacting of tri-roll press machine and leading for dragger
Draw, can be obtained with a thickness of 1.6mm, conductive functional layers and complex functional layer Thickness ratio are 1:1, the compound function that the number of plies is 1025 layers
The flaky composite material that ergosphere-conductive functional layers-complex functional layer is arranged alternately, outermost layer are complex functional layer (see figure 1).Institute
Composite material obtained has both excellent electromagnetic shielding performance and heating conduction.Electric performance test is the results show that the material is being put down
Row all has electric conductivity in bed boundary direction and perpendicular to bed boundary direction, and being parallel to bed boundary direction conductivity is 56 S/m,
It is 28S/m perpendicular to bed boundary direction conductivity；Electromagnetic shielding performance test display, X-band masking value reach 57dB；Thermal conductivity
Energy test result shows that thermal conductivity reaches 3.0W/ (mK).
Comparative example 5
As a comparison, in second step, the master batch being added in two extruders (A, B) is exchanged, other are the same as embodiment 5.I.e.
The final sheet material is that conductive functional layers-complex functional layer-conductive functional layers are arranged alternately structure, and outermost layer is conductive functional layers
(see figure 1).It is computed, material overall thickness is 1.6mm, and conductive functional layers and complex functional layer Thickness ratio are 1:1, the number of plies 1025
Layer.Electric performance test the results show that the material is being parallel to bed boundary direction and is all having electric conductivity perpendicular to bed boundary direction,
Being parallel to bed boundary direction conductivity is 50 S/m, is 20S/m perpendicular to bed boundary direction conductivity；；Electromagnetic shielding performance is surveyed
Examination display, X-band masking value reach 48dB；Heating conduction test result shows that thermal conductivity reaches 3.1W/ (mK).Thus may be used
See, the present invention can regulate and control the electricity of the multilayer material by changing the initial configuration of alternately stratified material according to actual needs
Conductance, electromagnetic shielding and heating conduction.
Embodiment 6
(1) raw material is thermoplastic polyurethane (TPU) (58A, BASF), carbon fiber (CF), ammonium polyphosphate (APP), conductive function
Ergosphere is carbon fiber filled thermoplastic's polyurethane, complex functional layer is carbon fiber and the composite filled thermoplastic poly ammonia of ammonium polyphosphate
Ester.It is dried using preceding raw material is placed in 80 DEG C of vacuum drying ovens for 24 hours to remove moisture.Conductive functional layers and compound function are prepared first
TPU and the CF melting mixing in double screw extruder after drying is granulated by ergosphere master batch, and temperature is 185 DEG C, is prepared and contains
The TPU/CF compound master batch of 10wt%CF；TPU and CF, APP melting mixing in double screw extruder after drying is granulated,
Temperature is 185 DEG C, and the TPU/CF/APP compound master batch containing 5wt%CF, 20wt%APP is prepared；
(2) conductive functional layers and complex functional layer master batch are put into two extruders (A, B) of multilayer extrusion system respectively
In (see figure 1), the rotating ratio 1:1 of extruder is adjusted, extruder temperature of each section is controlled respectively at 175 DEG C -180 DEG C -185 DEG C -185
℃.After material melts plasticizing in extruder, overlap two strands of melts in the junction station C of two runners, obtaining the number of plies is 2 layers
Initial configuration, then from rectangularl runner after the cutting of 6 layer multiplier D and layering superposition, outlet mold E in flow out, wherein converging
Flow device C, the temperature of layer multiplier D and outlet mold E is 185 DEG C or so, compacting and dragger using tri-roll press machine
Traction can be obtained with a thickness of 1.6mm, and conductive functional layers and complex functional layer Thickness ratio are 1:1, the sheet that the number of plies is 128 layers
Alternately laminar composite.
Comparative example 6-1
As a comparison, 6 second step middle outlet mould E thickness of embodiment is become into 0.2mm, other are the same as embodiment 6.It finally obtains
With a thickness of 0.2 mm, conductive functional layers and complex functional layer Thickness ratio are 1:1, and the alternating stratiform that the number of plies is 128 layers is electromagnetically shielded
Film.It can be seen that the present invention can according to actual needs, the thickness by changing outlet mold is prepared with different thickness
Electromagnetic shielding material.
Comparative example 6-2
As a comparison, 6 second step middle outlet mould E of embodiment is changed to the porous outlet mold for being 0.1mm with internal diameter, other
With embodiment 6.Finally obtaining diameter is 0.1 mm, and conductive functional layers and complex functional layer Thickness ratio are 1:1, and the number of plies is 128 layers
Alternating Fiber Laminated.It can be seen that the present invention can according to actual needs, the shape by changing outlet mold, which is prepared, to be had
The fibrous material of electromagnetic shielding performance.
Claims (6)
1. a kind of novel and multifunctional polymer-based multilayer electromagnetic shielding material, it is characterised in that the polymer-based multilayer electromagnetic screen
Covering material is by the material of following polymer-based conductive functional layers and the material of polymer-based complex functional layer respectively through extruder
Fusion plastification squeezes out, and after junction station exit is superimposed together and to form following initial configuration, using with the junction station
The multiple stratiform overlapping of the several layers multiplier of connection acts on, the extrudate that multilayered structure is arranged alternately with two-phase of formation:
(1) material of the polymer-based conductive functional layers is the polymer-based conducing composite material particle-filled by conducting function；(2)
The material of the polymer-based complex functional layer is the polymer-based conducing composite material particle-filled by complex function, in which:
The complex function particle is mixed by conducting function particle and other functional particles；(3) initial configuration can be by
The two-layer structure that polymer-based conductive functional layers and polymer-based complex functional layer are formed by stacking, or by polymer-based conduction
The three-decker that functional layer, polymer-based complex functional layer, polymer-based conductive functional layers are formed by stacking, or by macromolecule
The three-decker that base complex functional layer, polymer-based conductive functional layers, polymer-based complex functional layer are formed by stacking；
Macromolecule matrix in the polymer-based multilayer electromagnetic shielding material is selected from polyethylene, polypropylene, polyvinyl chloride, gathers
Methyl methacrylate, polystyrene, Kynoar, polyamide, polyester, polyformaldehyde, polyurethane, styrene analog thermoplastic bullet
Property body, polyester-type thermoplastic elastomer, polyolefins thermoplastic elastomer, polyacrylate analog thermoplastic elastomer, the third rubber of second
One of glue, butadiene-styrene rubber, neoprene, silicon rubber, fluorubber, natural rubber are a variety of；Wherein, described polymer-based to lead
Macromolecule matrix in electric functional layer and the polymer-based complex functional layer is same in above-mentioned material or not
It is of the same race；
Conducting function particle in the polymer-based conductive functional layers is metal, carbon black, carbon nanotube, graphene, carbon fiber
One of or a variety of, mass fraction 0.01-60%；
Conducting function particle in the polymer-based complex functional layer is metal, carbon black, carbon nanotube, graphene, carbon fiber
One of or it is a variety of, other functional particles be do not include above-mentioned the spherical, fibrous of conducting function particle, sheet, different form
One of inorganic particulate or organic filler are a variety of；The quality of complex function particle point in the polymer-based complex functional layer
Number is 0.01-60%, and the mass fraction of conducting function particle is 0.01-99.9% in complex function particle.
2. the novel and multifunctional polymer-based multilayer electromagnetic shielding material of one kind described in accordance with the claim 1, it is characterised in that institute
Polymer-based multilayer electromagnetic shielding material is stated to be parallel to bed boundary direction and all having electrical conductance perpendicular to bed boundary direction, and
And conductivity, electromagnetic shielding performance and other complex functions can pass through functional particles content, Thickness ratio, the number of plies, functional particles
Partial size, alternately one of initial configuration of stratified material or various ways are regulated and controled.
3. the novel and multifunctional polymer-based multilayer electromagnetic shielding material of one kind described in accordance with the claim 1, it is characterised in that institute
Stating extrudate is by two extruders (A, B), junction station (C), several layers multiplier (D), outlet mold (E) and cooling tractor
(F) the multilayer extrusion system formed is prepared by melting extrusion, and performance can overall thickness by the extrudate, total layer
The thickness of several, polymer-based conductive functional layers and polymer-based complex functional layer is regulated and controled than the loading of, functional particles,
In: the overall thickness of extrudate is 0.01-10mm；Total number of plies number is 2-32769；The polymer-based conductive functional layers and high score
The thickness ratio of subbase complex functional layer is 1:99-99:1.
4. the novel and multifunctional polymer-based multilayer electromagnetic shielding material of one kind described in accordance with the claim 1, it is characterised in that institute
The number of plies for stating extrudate initial configuration can regulate and control runner number by the switch in the junction station (C): 2 runners
The initial configuration that obtained initial configuration is 2 layers, 3 runners obtain is 3 layers.
5. the novel and multifunctional polymer-based multilayer electromagnetic shielding material of one kind described in accordance with the claim 1, it is characterised in that institute
The number of plies for stating extrudate can be regulated and controled in the following way by the initial configuration number of plies and layer multiplier number: (1) when initial
Structure is 2 layers, and when n layer multiplier of use, the number of plies of extrudate is 2(n+1)Layer, in which: n 0-14；(2) work as initial configuration
It is 3 layers, and when n layer multiplier of use, the number of plies of extrudate is 2(n+1)+ 1 layer, in which: n 0-14.
6. the novel and multifunctional polymer-based multilayer electromagnetic shielding material of one kind described in accordance with the claim 1, it is characterised in that root
Needing material obtained according to practical application is film, sheet material, plate, special section, fiber.
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