CN106566226A - Thermoplastic polyurethane/graphene foam material and preparation method and application thereof - Google Patents
Thermoplastic polyurethane/graphene foam material and preparation method and application thereof Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/02—Elements
- C08K3/04—Carbon
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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
- B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
- B32B37/12—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by using adhesives
- B32B37/1284—Application of adhesive
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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
- B32B38/00—Ancillary operations in connection with laminating processes
- B32B38/16—Drying; Softening; Cleaning
- B32B38/164—Drying
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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
- B32B5/00—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts
- B32B5/22—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by the presence of two or more layers which are next to each other and are fibrous, filamentary, formed of particles or foamed
- B32B5/32—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by the presence of two or more layers which are next to each other and are fibrous, filamentary, formed of particles or foamed at least two layers being foamed and next to each other
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- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/28—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof by elimination of a liquid phase from a macromolecular composition or article, e.g. drying of coagulum
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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
- B32B2250/22—All layers being foamed
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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
- B32B2255/00—Coating on the layer surface
- B32B2255/10—Coating on the layer surface on synthetic resin layer or on natural or synthetic rubber layer
- B32B2255/102—Coating on the layer surface on synthetic resin layer or on natural or synthetic rubber layer synthetic resin or rubber layer being a foamed layer
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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
- B32B2255/00—Coating on the layer surface
- B32B2255/26—Polymeric coating
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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
- B32B2266/00—Composition of foam
- B32B2266/02—Organic
- B32B2266/0207—Materials belonging to B32B25/00
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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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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2375/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
- C08J2375/04—Polyurethanes
- C08J2375/06—Polyurethanes from polyesters
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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- C08J2375/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
- C08J2375/04—Polyurethanes
- C08J2375/08—Polyurethanes from polyethers
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- C08L2203/00—Applications
- C08L2203/14—Applications used for foams
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
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- C08L2203/16—Applications used for films
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- C—CHEMISTRY; METALLURGY
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- C08L2207/04—Thermoplastic elastomer
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Abstract
The invention discloses a thermoplastic polyurethane/graphene foam material and a preparation method and application thereof. The thermoplastic polyurethane/graphene foam material has high electromagnetic shielding effectiveness and high wave absorbing performance. According to the method, firstly, single-layer thermoplastic polyurethane/graphene microfoam films are prepared through a phase separation method, then, the single-layer thermoplastic polyurethane/graphene microfoam films with the different graphene contents are bonded into an integrated material through glue, and therefore gradient dispersion of graphene in the thermoplastic polyurethane/graphene foam material is achieved. The gradient structure can endow the thermoplastic polyurethane/graphene foam material with good shielding effectiveness and meanwhile can greatly improve the wave absorbing performance of the material, and the prepared light thermoplastic polyurethane/graphene foam material has good application prospects in the fields of electromagnetic shielding and wave absorbing materials.
Description
Technical field
The invention belongs to polymer matrix electromagnetic shielding material field, more particularly to a kind of thermoplastic polyurethane/Graphene
Foam material and its preparation method and application.
Background technology
Electromagnetic Interference refers to that harmful electromagnetic wave makes the normal function of electronic device be interfered or cause showing for obstacle
As, abbreviation EMI (electromagnetic interference), refer to radio wave, magnetic wave, light wave, sunspot and its
It some from space natural disturbance.With the fast development of modern electronics industry, various wireless communication systems and high-frequency electrical
Sharply increasing for sub- number of devices, result in increasing for electromagnetic interference phenomenon outstanding day by day with electromagnetic pollution problem.On the one hand,
Electromagnetic radiation can cause severe jamming to the electronic equipment of surrounding, make their working procedure get muddled, and produce mistake
Action；Also, electromagenetic wave radiation can cause information leakage, the information security for making the instruments such as computer is subject to serious impact.It is existing
Not only there is interference to electronic device in discovery electromagnetic radiation, harm also can be produced to human body.The disease incidences such as cancer, leukemia
The increase of raising and electromagnetic radiation have certain relation.At present, how international organization and national governments, scientific research circle etc. are to prevent
Electromagnetic Interference gives great attention, and has formulated strict regulation and carry out trapped electromagnetic wave radiation capacity.Therefore, explore efficient
Electromagnetic shielding material, prevents electromagnetic radiation pollution with environmental protection and health, it has also become problem in the urgent need to address.
The most frequently used effective method of preventing and treating electromagnetic radiation is for harmful electromagnetic wave is shielded using electromagnetic shielding material
Cover.Therefore exploitation High Performance Shielding material is significant.The definition of material electromagnet shield effect is incident electromagnetic wave
Intensity and transmitted electromagnetic wave intensity rate logarithm, unit is dB.Electromagnet shield effect numerical value is higher to mean fewer electricity
Magnetic wave can penetrate shielding material.For example, the minimum electromagnet shield effect that business application is required is 20dB, it is meant that only 1%
Electromagnetic wave can penetrate shielding material.
There is the shortcomings of high perishable, density, difficult processing in traditional Metal Substrate shielding material, Graphene is a kind of new
Two-dimensional nano-carbon material, with good conduction, heat conduction and capability of electromagnetic shielding, itself and polymer mixed can be prepared soft
Tough composite of good performance, is expected to become the succedaneum of metal material.Foaming structure is introduced in polymer composites
The density and processing cost of such material can further be reduced.Meanwhile, loose structure can also induce electromagnetic wave in material
Portion carries out multipath reflection and scattering, increases its absorption to electromagnetic wave.So, it is commonly used for radar absorbing and shielded anechoic chamber etc.
Field.
In fact, material mainly includes reflecting and absorbing two kinds to shielding electromagnetic waves mechanism.However, most at present
Mainly by adding the conductive filler of high-load, to reach industrialized standard, (shield effectiveness is not less than polymeric barrier material
20dB), such as document：Adv.Funct.Mater.,2016,26,303-310；Carbon,2016,96,768-777；
Adv.Mater.2005,17,1999-2003.As a result, too high conductive filler makes its reflection to electromagnetic wave significantly strengthen, and draws
Send out the secondary pollution to environment.In order to improve this situation, the present invention by foaming structure, provide in combination with gradient-structure by preparation
There is the lightweight thermoplastic polyurethane/graphene composite material of good flexibility, excellent electromagnetic shield effectiveness and high absorbing property.
The content of the invention
The technical purpose of the present invention is to provide a kind of thermoplastic polyurethane/Graphene expanded material and preparation method thereof and answers
With the thermoplastic polyurethane/Graphene expanded material has excellent electromagnetic shield effectiveness and high absorbing property, can using the method
To realize the extensive preparation of polymer matrix composite, with good market application foreground.
A kind of preparation method of thermoplastic polyurethane/Graphene expanded material, including：
(1) disperse graphene in organic solvent, to add and must mix molten after Polyurethane Thermoplastic Elastomer stirring and dissolving
Liquid, mixed solution is poured in coagulating bath carries out precipitating, and the thermoplastic polyurethane/Graphene mixture of precipitation is dried rear powder
It is broken；
(2) thermoplastic polyurethane obtained in step (1)/Graphene mixture is dissolved in organic solvent, is mixed
Alloying film liquid, film is carried out with scraper and is separated, and obtains being done after thermoplastic polyurethane/Graphene fretting map thin film
It is dry；
(3) thermoplastic polyurethane obtained in step (2)/Graphene fretting map thin film is carried out into multiple-layer stacked, layer and layer
Between use glue bonding, formed integration thermoplastic polyurethane/Graphene expanded material.
In step (1), the Polyurethane Thermoplastic Elastomer is polyester-type or polyether-type.
In step (1), the organic solvent be N, N'- dimethylformamides (DMF), N, N'- dimethyl acetylamide
(DMAc), one or more in acetone, Ketohexamethylene and butanone.
In step (1), the coagulating bath is water or at least one in ethanol.
In the mixed solution of step (1), the mass ratio of the Graphene, Polyurethane Thermoplastic Elastomer and organic solvent is
1～30：70～99：1000～2500.
In step (2), the phase separation includes：By mixed solution pour into scraper carry out film and be exposed to temperature for 0～
50 DEG C and relative humidity are to carry out in the environment of 50～99%, and the time of the phase separation is 0.1～24h.
In step (2), the thickness of the mixing casting solution is 0.001～5mm.
In step (2), the pore size of the thermoplastic polyurethane/Graphene fretting map thin film is 1～15 μm, and thickness is
100～400 μm.
In step (2), described baking temperature is 20～80 DEG C.
In step (3), the glue is one or more in PU glue, epoxy glue and UV glue.
In step (3), the thermoplastic polyurethane/Graphene expanded material is by 2～100 layers of the poly- ammonia of monolayer thermoplastic
Ester/Graphene fretting map thin film is formed by stacking.
Further preferably, in step (3), the thermoplastic polyurethane/Graphene expanded material is by 2～100 layers of monolayer
Thermoplastic polyurethane/Graphene fretting map thin film by Graphene in matrix content it is incremented by successively, be first incremented by and successively decrease afterwards or first pass
The constant rule successively decreased again is overlapped after increasing, forms gradient-structure.According to impedance matching principle, when electromagnetic wave is from air incidence
During to polymer composites surface, the change of its inner conductive packing density gradient advantageously reduces electromagnetic wave in material surface
Reflection, increase its absorption in material internal.
Present invention also offers a kind of thermoplastic polyurethane/Graphene expanded material, the thermoplastic polyurethane/Graphene
Expanded material is prepared by said method.
The present invention also provides above-mentioned thermoplastic polyurethane/application of the Graphene expanded material in electromagnetic shielding field.
The present invention also provides above-mentioned thermoplastic polyurethane/application of the Graphene expanded material in absorbing material field.
Compared with prior art, the present invention has the advantages that：
(1) thermoplastic polyurethane/Graphene fretting map thin film with high Graphene content is prepared using phase separation method, gram
Take conventional physical foaming (fast pressure relief and the method that is rapidly heated) to be difficult to prepare the difficulty of the expanded material of high filler content；
(2) by foaming structure in combination with gradient-structure, the weight and cost of shielding material is not only significantly reduced, is also carried
High its absorption loss to electromagnetic wave；
(3) using phase separation method be capable of achieving monolayer thermoplastic polyurethane/Graphene fretting map thin film continuous prodution and
It is extensive to prepare, had using the integrated thermoplastic polyurethane/Graphene expanded material prepared by layer stackup addition itself good
Pliability well and autohension, the sealing member that can serve as in electromagnetic shielding device has higher market application foreground.
Description of the drawings
Fig. 1 is that the Graphene content that the embodiment of the present invention 1 is prepared is micro- for the thermoplastic polyurethane/Graphene of 4wt.%
The scanning electron microscope (SEM) photograph of foamed thin sheet；
Fig. 2 is the double-deck thermoplastic polyurethane/Graphene with Graphene Concentraton gradient prepared by the embodiment of the present invention 1
The shield effectiveness of composite prepared by expanded material and comparative example 1 in Ku wave bands (12～18GHz)；
Fig. 3 is the double-deck thermoplastic polyurethane/Graphene with Graphene Concentraton gradient prepared by the embodiment of the present invention 1
Composite prepared by expanded material and comparative example 1 is in Ku wave bands to electromagnetic wave absorptivity and the comparison diagram of reflectance；
Fig. 4 is with Graphene Concentraton gradient three layers of thermoplastic polyurethane/Graphene prepared by the embodiment of the present invention 4
The shield effectiveness of composite prepared by expanded material and comparative example 4 in Ku wave bands；
Fig. 5 is with Graphene Concentraton gradient three layers of thermoplastic polyurethane/Graphene prepared by the embodiment of the present invention 4
Composite prepared by expanded material and comparative example 4 is in Ku wave bands to electromagnetic wave absorptivity and the comparison diagram of reflectance.
Specific embodiment
The present invention is specifically described with reference to the accompanying drawings and examples.
Embodiment 1
(1) during the Graphene of 0.83g to be added the DMF of 300mL, ultrasonic disperse 10 minutes obtains black suspension.It is outstanding at this
20g Polyurethane Thermoplastic Elastomer particles are added in supernatant liquid, in 60 DEG C of oil bath high speed stirring and dissolving 5 hours, then by gained
To mixed solution pour precipitating in distilled water into.Finally, the thermoplastic polyurethane of precipitation/Graphene mixture is placed in into 60 DEG C
48h is dried in vacuum drying oven, crushes standby after taking-up；
(2) thermoplastic polyurethane in step (1)/Graphene mixture is re-dissolved in being mixed in the DMF of 100mL
Casting solution, is poured in the slot scraping of scraper and carries out film on clean glass plate, and blade thickness is set as 4mm.Complete
Afterwards, it is placed in 3h in the air that relative humidity is 80% under room temperature, is then taken out and is placed in being done in 30 DEG C of vacuum drying oven
Dry 24h, obtains thermoplastic polyurethane/Graphene fretting map thin film that Graphene content is 4wt.%, is labeled as PUG4, its scanning
Electron microscope is as shown in Figure 1.
By same method prepare Graphene content be 8,12,16, the thermoplastic polyurethane/Graphene of 20wt.%
Fretting map thin film, and it is respectively labeled as PUG8, PUG12, PUG16, PUG20.All thermoplastic polyurethanes prepared by the method/
Graphene fretting map thin film all has similar density (0.42g/cm3) and thickness (2mm).
(3) PUG12 the and PUG20 bi-materials prepared in selecting step (2) press Graphene content order from small to large
Bondd with PU glue, formed the double-deck thermoplastic polyurethane/Graphene expanded material with Graphene Concentraton gradient.
Comparative example 1
Two-layer PUG16 prepared in embodiment 1 is bondd.
Because the monolayer material for constituting multilayer materials is different, there is more permutation and combination in different monolayer materials again
Mode.So, the electromagnetic shielding test process of multilayer materials is typically more complicated.In view of above-mentioned reason.It is of the invention first
Shielding propertiess and absorbing property to the polyurethane of the two layers of thermoplastic with gradient-structure/graphene composite material launch research,
And then spread to three layers of thermoplastic polyurethane/graphene composite material.
Because the similar density of the thermoplastic polyurethane/grapheme foam prepared by phase separation method, facilitates MULTILAYER COMPOSITE
During gradient-structure and homogeneous texture design.By taking PUG12, PUG16, PUG20 in embodiment 1 as an example, monolayer PUG12 and
PUG20 is combined the material that the content of Graphene is combined with two-layer monolayer PUG16 in resulting double-layer composite material (embodiment 1)
(comparative example 1) is equal.Therefore, it is in gradient that PUG12 and PUG20 is combined Graphene in resulting double layer material in embodiment 1
Scattered, it is homodisperse that bilayer PUG16 is combined Graphene in resulting material in comparative example 1.Similar structure design
Theory is equally applicable in below example and comparative example.
Additionally, for the double-deck thermoplastic polyurethane/grapheme foam in embodiment 1, it exists in test process
Two kinds of situations：(1) by the incidence of PUG12 faces, through the injection of PUG20 faces, (situation is referred to as positive gradient to electromagnetic wave, in figs. 2 and 3
It is labeled as 12-20)；(2) electromagnetic wave is incident by PUG20 faces, project through PUG12 faces (situation is referred to as negative gradient, in Fig. 2 and
20-12 is labeled as in Fig. 3).It is two-layer phase due to double-deck thermoplastic polyurethane/graphene composite material is constituted in comparative example 1
Same PUG16, therefore, it only exists a kind of situation, the i.e. incidence of PUG16 faces in test process and projects through PUG16 faces, should
Situation is labeled as in figs. 2 and 3 16-16.Finally, to two kinds of composites prepared in above-described embodiment 1 and comparative example 1
Three kinds of situations capability of electromagnetic shielding test is carried out using vector network analyzer.Their screens in Ku wave bands (12～18GHz)
Efficiency is covered as shown in Fig. 2 corresponding electromagnetic wave absorptivity and reflectivity comparison diagram is as shown in Figure 3.
As a result show：(1) gradient-structure has no significant effect to the shield effectiveness of multilayer materials, (right with positive gradient
Answer the 12-20 in embodiment 1) and negative gradient (correspondence 20-12 in embodiment 1) structure two kinds of thermoplastic polyurethane/graphite
The electromagnet shield effect curve of alkene double-layer composite material essentially coincides (～23-31dB) and～2dB slightly higher compared with comparative example 1；(2) ladder
Degree structure has considerable influence to the absorbing property of multilayer materials, and positive gradient structure is compared with negative gradient structure to incoming electromagnetic wave energy
The high 10-15% of absorbance of amount, the low 10-15% of reflectance；(3) for compared with comparative example 1, positive gradient structure is to incoming electromagnetic wave energy
The absorbance of amount improves 6～10%, reflectance reduction 6～10%；By contrast, the double-deck thermoplastic with negative gradient structure
The absorbing property of property polyurethane/Graphene expanded material is compared with comparative example 1 low 6～7%, and reflectance is high by 6～7%.
In view of the stronger absorbing property in multilayer materials of positive gradient structure, just with positive ladder in following examples
The multilayer materials of degree structure test their electromagnetic shielding and absorbing property as a class preference.
Embodiment 2
Material therefor in the present embodiment is PUG8 and PUG16 prepared in embodiment 1, and they are pressed into Graphene content
Order from small to large is bondd with PU glue, forms the double-deck thermoplastic polyurethane/graphite with Graphene Concentraton gradient
Alkene expanded material.
Comparative example 2
Two-layer PUG12 prepared in embodiment 1 is bondd.
Electromagnetic wave shielding is carried out using vector network analyzer to two kinds of composites prepared by embodiment 2 and comparative example 2
Can test.As a result show：(1) the two kind of shield effectiveness of composite in Ku wave bands is 23～24dB, and gradient-structure is to more
The shield effectiveness of layer composite has no significant effect；(2) thermoplastic polyurethane with positive gradient structure/Graphene expanded material
In Ku wave bands 10～12% is improve compared with comparative example 2 to the absorbance of incoming electromagnetic wave energy, reflectance reduction 10～
12%.
Embodiment 3
Material therefor in the present embodiment is PUG4 and PUG12 prepared in embodiment 1, and they are pressed into Graphene content
Order from small to large is bondd with PU glue, forms the double-deck thermoplastic polyurethane/graphite with Graphene Concentraton gradient
Alkene expanded material.
Comparative example 3
Two-layer PUG8 prepared in embodiment 1 is bondd.
Electromagnetic wave shielding is carried out using vector network analyzer to two kinds of composites prepared by embodiment 3 and comparative example 3
Can test.As a result show：(1) the two kind of shield effectiveness of composite in Ku wave bands is 15～18dB, and gradient-structure is to more
The shield effectiveness of layer composite has no significant effect；(2) the double-deck thermoplastic polyurethane with positive gradient structure/Graphene foaming
Material improves 5～20% to the absorbance of incoming electromagnetic wave energy in Ku wave bands compared with comparative example 4, and reflectance reduction 5～
20%.
Embodiment 4
Material therefor in the present embodiment is PUG4, PUG8 and PUG12 prepared in embodiment 1, and they are pressed into PUG4 │
PUG8 │ PUG12 and PUG4 │ PUG12 │ PUG8 orders are bondd with PU glue, are formed two kinds and are had Graphene Concentraton gradient
Three layers of thermoplastic polyurethane/Graphene composite foam material.
Comparative example 4
The three layers of PUG8 prepared in embodiment 1 are bondd.
Finally, vector net is adopted to three kinds of situations of three kinds of composites prepared in above-described embodiment 4 and comparative example 4
Network analyser carries out capability of electromagnetic shielding test.It is main for three layers of thermoplastic polyurethane/grapheme foam in embodiment 4
Test two kinds of situations：(1) electromagnetic wave is incident by PUG4, through PUG8, from PUG12 (the positive ladder in correspondence Fig. 4 and Fig. 5 is projected
Degree, is labeled as 4-8-12)；(2) electromagnetic wave is incident by PUG4, through PUG12, projects from PUG8 (double in correspondence Fig. 4 and Fig. 5
Gradient, is labeled as 4-12-8).Because the sample in comparative example 4 is three layers of PUG8 composites, it is only existed in test process
A kind of situation, is labeled as in figures 4 and 5 8-8-8.Finally, they in the shield effectiveness of Ku wave bands as shown in figure 4, corresponding
Electromagnetic wave absorptivity and reflectivity comparison diagram it is as shown in Figure 5.
As a result show：(1) the three kind of shield effectiveness of composite in Ku wave bands is 18～26dB, and gradient-structure is to more
The shield effectiveness of layer composite has no significant effect；(2) gradient-structure affects larger to the absorbing property of multilayer materials,
With double gradient-structures three layers of thermoplastic polyurethane/Graphene expanded material is in Ku wave bands to the suction of incoming electromagnetic wave energy
Yield improves 15～20% compared with comparative example 4, reflectance reduction 15～20%；(3) three layers of thermoplastic with positive gradient structure
Property polyurethane/Graphene expanded material improves 5 compared with comparative example 4 in Ku wave bands to the absorbance of incoming electromagnetic wave energy～
10%, reflectance reduction 5～10%.In view of double gradients and positive gradient structure are in terms of multilayer materials absorbing property is improved
Advantage, the present invention be just applied to them as two kinds of preferred structures in following examples.
Embodiment 5
Material therefor in the present embodiment is PUG8, PUG12 and PUG16 prepared in embodiment 1, and they are pressed into PUG8
The order of │ PUG12 │ PUG16 (positive gradient structure) and PUG8 │ PUG16 │ PUG12 (double gradient-structures) is bondd with PU glue,
Form the three layers of thermoplastic polyurethane/Graphene expanded material with Graphene Concentraton gradient.
Comparative example 5
The three layers of PUG12 prepared in embodiment 1 are bondd.
Electromagnetic wave shielding is carried out using vector network analyzer to three kinds of composites prepared by embodiment 5 and comparative example 5
Can test.As a result show：(1) the three kind of shield effectiveness of composite in Ku wave bands is 28～37dB, and gradient-structure is to more
The shield effectiveness of layer composite has no significant effect；(2) three layers of thermoplastic polyurethane with double gradient-structures/Graphene foaming
Material improves 17～20% to the absorbance of incoming electromagnetic wave energy in Ku wave bands compared with comparative example 5, reflectance reduction 17
～20%；(3) three layers of thermoplastic polyurethane/Graphene expanded material with positive gradient structure are in Ku wave bands to incoming electromagnetic
The absorbance of wave energy improves 12～20% compared with comparative example 5, reflectance reduction 12～20%.
Embodiment 6
Material therefor in the present embodiment is PUG12, PUG16 and PUG20 prepared in embodiment 1, and they are pressed
The order of PUG12 │ PUG16 │ PUG20 (positive gradient structure) and PUG12 │ PUG20 │ PUG16 (double gradient-structures) is entered with PU glue
Row bonding, forms two kinds of three layers of thermoplastic polyurethane/Graphene expanded materials with Graphene Concentraton gradient.
Comparative example 6
The three layers of PUG16 prepared in embodiment 1 are bondd.
Electromagnetic wave shielding is carried out using vector network analyzer to three kinds of composites prepared by embodiment 6 and comparative example 6
Can test.As a result show：(1) the three kind of shield effectiveness of composite in Ku wave bands is 32～45dB, and gradient-structure is to more
The shield effectiveness of layer composite has no significant effect；(2) three layers of thermoplastic polyurethane with double gradient-structures/Graphene foaming
Material improves 15～22% to the absorbance of incoming electromagnetic wave energy in Ku wave bands compared with comparative example 6, reflectance reduction 15
～22%；(3) three layers of thermoplastic polyurethane/Graphene expanded material with positive gradient structure are in Ku wave bands to incoming electromagnetic
The absorbance of wave energy improves 12～20% compared with comparative example 6, reflectance reduction 12～20%.
Claims (10)
1. the preparation method of a kind of thermoplastic polyurethane/Graphene expanded material, it is characterised in that include：
(1) disperse graphene in organic solvent, add and obtain after Polyurethane Thermoplastic Elastomer stirring and dissolving mixed solution, will
Mixed solution is poured in coagulating bath carries out precipitating, and the thermoplastic polyurethane/Graphene mixture of precipitation is crushed after being dried；
(2) thermoplastic polyurethane obtained in step (1)/Graphene mixture is dissolved in organic solvent, obtains mixing casting
Film liquid, film is carried out with scraper and is separated, and obtains being dried after thermoplastic polyurethane/Graphene fretting map thin film；
(3) thermoplastic polyurethane obtained in step (2)/Graphene fretting map thin film is carried out into multiple-layer stacked, between layers
With glue bonding, the thermoplastic polyurethane/Graphene expanded material of integration is formed.
2. the preparation method of thermoplastic polyurethane according to claim 1/Graphene expanded material, it is characterised in that step
Suddenly in the mixed solution of (1), the mass ratio of the Graphene, Polyurethane Thermoplastic Elastomer and organic solvent is 1～30：70～
99：1000～2500.
3. the preparation method of thermoplastic polyurethane according to claim 1/Graphene expanded material, it is characterised in that step
Suddenly in (2), the phase separation includes：Mixed solution poured into scraper carries out film and to be exposed to temperature for 0～50 DEG C and relative
Humidity is to carry out in the environment of 50～99%, and time of the phase separation is 0.1～24h；Described baking temperature is 20～80
℃。
4. the preparation method of thermoplastic polyurethane according to claim 1/Graphene expanded material, it is characterised in that step
Suddenly in (2), the thickness of the mixing casting solution is 0.001～5mm.
5. the preparation method of thermoplastic polyurethane according to claim 1/Graphene expanded material, it is characterised in that step
Suddenly in (2), the pore size of the thermoplastic polyurethane/Graphene fretting map thin film is 1～15 μm, and thickness is 100～400 μ
m。
6. the preparation method of thermoplastic polyurethane according to claim 1/Graphene expanded material, it is characterised in that step
Suddenly in (3), the thermoplastic polyurethane/Graphene expanded material is micro- by 2～100 layers of monolayer thermoplastic's polyurethane/Graphene
Foamed thin sheet is formed by stacking.
7. the preparation method of thermoplastic polyurethane according to claim 6/Graphene expanded material, it is characterised in that step
Suddenly in (3), the thermoplastic polyurethane/Graphene expanded material is micro- by 2～100 layers of monolayer thermoplastic's polyurethane/Graphene
Foamed thin sheet by Graphene in matrix content it is incremented by successively, be first incremented by successively decrease afterwards or first be incremented by after the constant rule successively decreased again enter
Row superposition.
8. a kind of thermoplastic polyurethane/Graphene expanded material, it is characterised in that the thermoplastic polyurethane/Graphene foaming
Method of the material according to any one of claim 1～7 is prepared.
9. a kind of application of thermoplastic polyurethane/Graphene expanded material, it is characterised in that the thermoplastic polyurethane/graphite
Application of the alkene expanded material in electromagnetic shielding field.
10. a kind of application of thermoplastic polyurethane/Graphene expanded material, it is characterised in that the thermoplastic polyurethane/graphite
Application of the alkene expanded material in absorbing material field.
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