CN111925630A - High-strength electromagnetic shielding and heat conducting PBT/PET nano composite material and preparation method thereof - Google Patents

High-strength electromagnetic shielding and heat conducting PBT/PET nano composite material and preparation method thereof Download PDF

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CN111925630A
CN111925630A CN202010706003.2A CN202010706003A CN111925630A CN 111925630 A CN111925630 A CN 111925630A CN 202010706003 A CN202010706003 A CN 202010706003A CN 111925630 A CN111925630 A CN 111925630A
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CN111925630B (en
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高珠怡
尚梦瑶
程亨伦
申屠宝卿
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Zhejiang University ZJU
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    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L67/00Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
    • C08L67/02Polyesters derived from dicarboxylic acids and dihydroxy compounds
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B82NANOTECHNOLOGY
    • B82YSPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00Nanotechnology for materials or surface science, e.g. nanocomposites
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B82NANOTECHNOLOGY
    • B82YSPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y40/00Manufacture or treatment of nanostructures
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    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00Use of inorganic substances as compounding ingredients
    • C08K3/18Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20Oxides; Hydroxides
    • C08K3/22Oxides; Hydroxides of metals
    • C08K2003/2265Oxides; Hydroxides of metals of iron
    • C08K2003/2275Ferroso-ferric oxide (Fe3O4)
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    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
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    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00Polymer mixtures characterised by other features
    • C08L2205/02Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
    • C08L2205/025Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
    • CCHEMISTRY; METALLURGY
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    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00Polymer mixtures characterised by other features
    • C08L2205/03Polymer mixtures characterised by other features containing three or more polymers in a blend

Abstract

The invention discloses a high-strength electromagnetic shielding and heat conducting PBT/PET nano composite material and a preparation method thereof, wherein the nano composite materialThe material comprises the following components in parts by weight: 70-80 parts of polybutylene terephthalate, 20-30 parts of polyethylene terephthalate, 5-10 parts of toughening agent and graphene-Fe3O45-10 parts of composite filler, 0.05-1 part of filler surface treating agent and 0.5-1.4 parts of antioxidant; graphene-Fe3O4The composite filler is prepared by carrying out chemical coprecipitation in a graphene stripping solution system after carrying out water phase stripping on graphene with different sheet diameters. The PBT/PET nano composite material prepared by the invention has excellent electromagnetic shielding effect through the synergistic effect of dielectric loss and magnetic loss, and the shielding mechanism mainly absorbs electromagnetic waves. In addition, the graphene with different sheet diameters improves the mechanical property of the material while forming a perfect electric and heat conducting network.

Description

High-strength electromagnetic shielding and heat conducting PBT/PET nano composite material and preparation method thereof
Technical Field
The invention belongs to the technical field of preparation of electromagnetic shielding and heat conducting composite materials, and relates to a high-strength electromagnetic shielding and heat conducting PBT/PET nano composite material and a preparation method thereof.
Background
With the rapid development of wireless communication technology, electronic communication equipment is widely used, which brings great convenience to the life of people. However, these electronic communication devices generate electromagnetic radiation during use, which not only causes electromagnetic interference and leakage of electromagnetic information between the devices, but also may cause harm to human health. At present, the main method for solving the problem of electromagnetic radiation is to shield and absorb electromagnetic waves by using an electromagnetic shielding material and convert the absorbed electromagnetic waves into joule heat dissipation. Among them, the conductive polymer composite material has become an important research and development direction in the field of electromagnetic shielding materials in recent years due to its characteristics of light weight, good processing formability, adjustable electromagnetic shielding performance and the like. The traditional electromagnetic shielding polymer composite material adopts carbon black, graphite, metal and the like as fillers, and in order to achieve an effective electromagnetic shielding effect, the mechanical property of the material is reduced due to the excessively high addition amount of the fillers. In recent years, two-dimensional carbon nanomaterial graphene has received much attention from researchers as a novel highly electrically and thermally conductive filler. The electron mobility of the graphene reaches 15000cm at normal temperature2·V-1·s-1The thermal conductivity is as high as 5300 W.m-1·K-1. However, graphene has high surface energy and strong pi-pi interaction between nanosheets, and is easy to agglomerate in a polymer matrix, so that the formation of an electric and heat conducting network in a system is not facilitated. In addition, the agglomeration causes the graphene filling amount to be too high, and the mechanical property of the material is adversely affected. Meanwhile, when graphene is singly added as a filler, the polymer composite material only realizes shielding of electromagnetic waves through dielectric loss, and the shielding efficiency is poor.Therefore, how to realize the combination of high electromagnetic shielding, high thermal conductivity and excellent mechanical properties of the electromagnetic shielding polymer composite material becomes a problem which needs to be solved urgently in industrial production.
The invention patent with application number CN110536596A discloses a magnetic nano carbon film for electromagnetic shielding and a preparation method thereof, and the steps comprise: A. grinding carbon nanotubes, graphene or carbon nanofibers, ultrasonically dispersing, dispersing by a high-pressure homogenizer, centrifuging to obtain a uniform and stable dispersion liquid, mixing the dispersion liquid, and performing vacuum filtration to prepare a carbon nanofiber film; B. combining the magnetic particle coating layer with the nano carbon film by using a codeposition method; C. the conductive polymer layer is prepared by a chemical oxidation process. Therefore, the preparation process of the electromagnetic shielding material is complex, the monomer in-situ polymerization reaction is carried out on the surface of the nano carbon film, the solvent dosage is large, and the green industrial production cannot be realized.
The invention patent with the application number of CN108976700A discloses a controllable preparation method of a high-stacking-degree graphene-based modified high-thermal-conductivity carbon-plastic alloy, which comprises the following components in percentage by weight: 5-50% of high-stacking-degree graphene filler, 30-55% of thermosetting resin, 0.2-2% of coupling agent, 1-5% of resin diluent, 7-15% of curing agent, 5-20% of reinforcing filler and 2-5% of auxiliary agent. The preparation method of the high-stacking-degree graphene filler comprises the following steps: A. mixing the two kinds of graphene, and adding the mixture into a medium containing a surfactant to prepare a graphene solution; B. mixing the two nano graphite micro-sheets, adding the mixture into a medium containing a surfactant, and preparing a nano graphite micro-sheet solution; C. mixing the graphene solution and the nano-graphite microchip solution, adding an interfacial compatilizer and a bridging agent, mixing and compounding to obtain a graphene mixed solution; D. and adding a viscosity regulator into the graphene mixed solution, uniformly stirring, and performing spray drying granulation to obtain the high-stacking-degree graphene heat-conducting filler. From the above, the preparation process of the high stacking graphene filler is complex, the added graphene is various, the addition amount of the filler in the material is large, and the cost is high.
Disclosure of Invention
The invention provides a high-strength electromagnetic shielding and heat conducting PBT/P (polybutylene terephthalate/polypropylene) for overcoming the defects in the prior artET nano composite material and its preparation method. The invention uses two graphene nanoplatelets with ten times difference of sheet diameter to form dispersion liquid, and the dispersion liquid and Fe are mixed in the dispersion liquid3O4Coprecipitation is carried out, so that the surface of the large-sheet-diameter graphene is coated with Fe3O4Nanoparticles of Fe3O4The nano particles introduce magnetic loss to strengthen the shielding effect on electromagnetic waves. Further, Fe3O4The existence of the graphene nano-sheet weakens the pi-pi acting force between the large-sheet-diameter graphene sheets, so that the aggregation of the graphene nano-sheets is inhibited. One part of the small-radius graphene is filled in the fracture of the large-radius graphene in heat conduction connection, so that an electric and heat conduction network is perfected, the other part of the small-radius graphene covers the large-radius graphene, the stress distribution is changed, cracks are expanded on the interface of the filler and the polymer, and finally, energy is dispersed on the surface of the large-radius graphene sheet layer, so that the mechanical property of the material is improved. The PBT/PET nano composite material obtained by the invention has excellent mechanical property, heat-conducting property and electromagnetic shielding property.
The invention is realized by the following technical scheme: a high-strength electromagnetic shielding and heat conducting PBT/PET nano composite material comprises the following components in parts by weight: 70-80 parts of polybutylene terephthalate, 20-30 parts of polyethylene terephthalate, 5-10 parts of toughening agent and graphene-Fe3O45-10 parts of composite filler, 0.05-1 part of filler surface treating agent and 0.5-1.4 parts of antioxidant; the graphene-Fe3O4The composite filler is prepared by the following method:
(1) adding large-sheet-diameter graphene nanoplatelets, small-sheet-diameter graphene nanoplatelets and sodium dodecyl benzene sulfonate into deionized water, and ultrasonically dispersing for 3-5 hours to prepare a graphene dispersion liquid; the mass ratio of the large-sheet-diameter graphene nanoplatelets to the small-sheet-diameter graphene nanoplatelets to the sodium dodecyl benzene sulfonate to the deionized water is 2-3:1:1.5-4: 300-.
(2) Adding ferric chloride hexahydrate and ferrous chloride tetrahydrate into deionized water to prepare a ferrous salt/ferric salt solution, wherein the mass ratio of the ferric chloride hexahydrate to the ferrous chloride tetrahydrate to the deionized water is 1-2:1: 40-60.
(3) Adding a ferrous salt/ferric salt solution into the graphene dispersion liquid, ultrasonically dispersing for 1-2h, adding ammonia water at the stirring speed of 700rpm and under the protection of nitrogen to adjust the pH value to about 8-10, heating to 40-60 ℃, and reacting for 1-2h, wherein the mass ratio of the ferrous salt/ferric salt solution to the graphene dispersion liquid is 1.7-2.6: 1.
(4) Cooling to room temperature after the reaction is finished, performing suction filtration, washing a filter cake to be neutral by using ethanol and deionized water, and drying at 70-90 ℃ for 6h to obtain graphene-Fe3O4And (4) composite filling.
Further, the thickness of the large-sheet-diameter graphene nanoplatelets is 5-100nm, and the particle size D is5090.0-130.0 μm, and more than 10 layers.
Further, the thickness of the small-aperture graphene nanoplatelets is 5-100nm, and the particle size D is5010.0-14.0 μm, and more than 10 layers.
Furthermore, the toughening agent is formed by mixing one or more of glycidyl methacrylate grafted ethylene-octene copolymer, maleic anhydride grafted styrene-ethylene-butene-styrene copolymer, methyl acrylate-butadiene-styrene copolymer and ethylene-methyl acrylate-glycidyl methacrylate copolymer according to any proportion.
Further, the filler surface treatment agent is formed by mixing one or more of a silane coupling agent KH560, a silane coupling agent KH550, a titanate coupling agent and methyl silicone oil according to any proportion.
Furthermore, the antioxidant is formed by mixing one or two of antioxidant 1010 and antioxidant 168 according to any proportion.
Further, the filler surface treatment agent and graphene-Fe3O4The mass ratio of the composite filler is 1-10: 100.
The invention also discloses a preparation method of the high-strength electromagnetic shielding and heat conducting PBT/PET nano composite material, which comprises the following steps:
(1) mixing graphene-Fe3O4The composite filler and the filler surface treating agent are uniformly mixed in a high-speed mixer;
(2) and (3) melting, blending and extruding the treated filler, polybutylene terephthalate, polyethylene terephthalate, toughening agent and antioxidant by using a double-screw extruder for granulation to obtain the high-strength electromagnetic shielding and heat-conducting PBT/PET nanocomposite material.
Further, in the step (2), the temperature of the barrel of the twin-screw extruder is 240-.
The invention has the beneficial effects that:
(1) according to the invention, a chemical coprecipitation reaction is carried out in the graphene dispersion liquid, and the stripped graphene large sheet layer is coated with Fe3O4Nanoparticles of Fe3O4The existence of the graphene nano-sheet weakens the pi-pi acting force between the large-sheet-diameter graphene sheets, inhibits the aggregation of the graphene nano-sheets, and improves the dispersion of the graphene nano-sheets in the matrix. In addition, magnetic loss is introduced on the basis of dielectric loss, and the electromagnetic shielding efficiency of the composite material is greatly improved.
(2) According to the invention, through compounding two nano graphene micro sheets with the sheet diameter difference of ten times, one part of small-diameter graphene is filled in the fracture of the large-diameter graphene heat conduction connection, the electric and heat conduction network is perfected, the other part of small-diameter graphene covers the large-diameter graphene, the stress distribution is changed, cracks are expanded on the interface of the filler and the polymer, and finally, energy is dispersed on the surfaces of the large-diameter graphene sheets, so that the mechanical property of the material is improved.
(3) The invention uses the sodium dodecyl benzene sulfonate as the dispersing agent of the graphene in the water solution and Fe3O4The dispersant in the coprecipitation process reduces the usage amount of the solvent. The prepared filler is wetted by the filler surface treating agent, so that the compatibility of the filler and a matrix is promoted, and the dispersibility of the filler is improved.
(4) The PBT/PET nano composite material obtained by the invention has excellent comprehensive properties, namely high strength, high electromagnetic shielding and high thermal conductivity. The experimental result of the embodiment shows that the PBT/PET nano composite material provided by the invention has the shielding effectiveness of 50dB and the thermal conductivity of more than or equal to 1.5 W.m-1·K-1
Detailed Description
The invention is further explained below with reference to specific examples, but the scope of protection described herein is not limited to the examples.
Example 1
A high-strength electromagnetic shielding and heat conducting PBT/PET nano composite material and a preparation method thereof are disclosed, which comprises the following components in parts by weight: 70 parts of polybutylene terephthalate, 30 parts of polyethylene terephthalate, 5 parts of glycidyl methacrylate grafted ethylene-octene copolymer and graphene-Fe3O45 parts of composite filler, KH 5600.5 parts of silane coupling agent, 10100.5 parts of antioxidant and 1680.5 part of antioxidant.
The graphene-Fe3O4The composite filler is prepared by the following specific steps:
(1) subjecting large-sheet-diameter graphene nanoplatelets (with thickness of 5-100nm and particle size D)5090.0-130.0 μm, more than 10 layers, small-diameter graphene nanoplatelets (5-100 nm in thickness and D in particle size)5010.0-14.0 μm, more than 10 layers) and sodium dodecyl benzene sulfonate are added into deionized water, the mass ratio is 2:1:3:350, and ultrasonic dispersion is carried out for 3-5h, thus obtaining graphene dispersion liquid;
(2) adding ferric chloride hexahydrate and ferrous chloride tetrahydrate into deionized water in a mass ratio of 2:1:60 to prepare a ferrous salt/ferric salt solution;
(3) adding a ferrous salt/ferric salt solution into the graphene dispersion liquid according to the mass ratio of 1.7:1, performing ultrasonic dispersion for 1-2h, adding ammonia water at the stirring speed of 700rpm under the protection of nitrogen to adjust the pH value to about 8-10, and heating to 40-60 ℃ for reaction for 1-2 h.
(4) Cooling to room temperature after the reaction is finished, performing suction filtration, washing a filter cake to be neutral by using ethanol and deionized water, and drying at 70-90 ℃ for 6h to obtain graphene-Fe3O4And (4) composite filling.
The preparation method of the high-strength electromagnetic shielding and heat conducting PBT/PET nano composite material comprises the following steps:
5 parts of graphene-Fe3O4Uniformly mixing the composite filler and 0.5 part of silane coupling agent KH560 in a high-speed mixer;
and (3) melting and blending the treated filler, 70 parts of polybutylene terephthalate, 30 parts of polyethylene terephthalate, 5 parts of glycidyl methacrylate grafted ethylene-octene copolymer, 0.5 part of antioxidant 1010 and 0.5 part of antioxidant 168 by using a double-screw extruder (the temperature of a charging barrel is 240-260 ℃ and the rotating speed of a screw is 300rpm), and extruding and granulating to obtain the high-strength electromagnetic shielding and heat conducting PBT/PET nanocomposite.
Example 2
The method of this example is substantially the same as that of example 1, except that: the additive amount of the polybutylene terephthalate is 80 parts, and the additive amount of the polyethylene terephthalate is 20 parts.
Example 3
The method of this example is substantially the same as that of example 1, except that: the addition amount of the glycidyl methacrylate grafted ethylene-octene copolymer is 10 parts.
Example 4
The method of this example is substantially the same as that of example 1, except that: the graphene-Fe3O4The addition amount of the composite filler is 8 parts.
Example 5
The method of this example is substantially the same as that of example 1, except that: the graphene-Fe3O4The addition amount of the composite filler is 10 parts.
Example 6
The method of this example is substantially the same as that of example 1, except that: the mass ratio of the large-sheet-diameter graphene nanoplatelets to the small-sheet-diameter graphene nanoplatelets to the sodium dodecyl benzene sulfonate to the deionized water is 1:1:3: 350.
Example 7
The method of this example is substantially the same as that of example 1, except that: the mass ratio of the ferrous salt/ferric salt solution to the graphene dispersion liquid is 2.6: 1.
Comparative example 1
The process of this comparative example is essentially the same as example 1, except that: without addition of graphene-Fe3O4And (4) composite filling.
Comparative example 2
The process of this comparative example is essentially the same as example 1, except that: without addition of graphene-Fe3O4And (3) compounding the filler, and adding 10 parts of large-sheet-diameter graphene nanoplatelets.
Comparative example 3
The process of this comparative example is essentially the same as example 1, except that: preparation of graphene-Fe3O4The large-sheet-diameter graphene nanoplatelets and small-sheet-diameter graphene nanoplatelets are not added in the step (1) of composite filler, and the chemical coprecipitation Fe is prepared3O4Nano particles, 4 parts of prepared Fe3O4The PBT/PET nano composite material is prepared by taking the nano particles, 4 parts of large-sheet-diameter graphene micro sheets and 2 parts of small-sheet-diameter graphene micro sheets as fillers.
Comparative example 4
The process of this comparative example is essentially the same as example 1, except that: the additive amount of the polybutylene terephthalate is 60 parts, and the additive amount of the polyethylene terephthalate is 40 parts.
Comparative example 5
The method of this example is substantially the same as that of example 1, except that: the addition amount of the glycidyl methacrylate grafted ethylene-octene copolymer is 15 parts.
Comparative example 6
The method of this example is substantially the same as that of example 1, except that: no filler surface treatment agent was added.
And (3) performance testing:
the PBT/PET nanocomposites prepared in examples 1-7 and comparative examples 1-6 above were subjected to a sample bar test using an injection molding machine,
(1) bending property test
The bending property of the sample is measured by using a universal material tester, and the test is carried out at room temperature according to the GB/T9341-2008 standard, and the size of the test sample is 80 multiplied by 10 multiplied by 4mm3The bending rate was 5 mm/min. Each group tested 5 splines and the test results averaged.
(2) Heat distortion temperature test
Using thermal deformation testersHDT of the test specimens, carried out according to GB/T1634.1-2004, the dimensions of the test specimens being 80X 10X 4mm3The initial temperature is 20 ℃, the heating rate is 120 ℃/h, and the testing pressure is 1.8 MPa. Each group tested 3 splines and the test results averaged.
(3) Cantilever beam impact strength test
The unnotched impact strength of the cantilever beam of the sample is tested by using an instrumented pendulum impact instrument, the test is carried out at room temperature according to GB/T1843-2008 standard, a 5.5J pendulum is used, and the size of the test sample is 80 multiplied by 10 multiplied by 4mm3. Each group tested 5 splines and the test results averaged.
(4) Thermal conductivity test
The thermal conductivity of the samples was measured using a thermal conductivity tester, performed at room temperature according to GB/T10297-3
(5) Electromagnetic shielding test
Using a vector network analyzer to test the electromagnetic shielding effectiveness of a sample, and adopting a waveguide method to measure the electromagnetic shielding effectiveness between 8.2 and 12.4GHz of an X-wave frequency band, wherein the size of the test sample is 23 multiplied by 10 multiplied by 4mm3
The test data are as follows:
Figure BDA0002594717870000061
Figure BDA0002594717870000071
as can be seen from the table, the mechanical properties, the thermal conductivity and the electromagnetic shielding properties of the examples 1 to 7 are superior to those of the comparative examples 1 to 6, which shows that the PBT/PET nanocomposite prepared by the invention has excellent comprehensive properties, namely high strength, high electromagnetic shielding and high thermal conductivity.
Examples 1, 2 and comparative example 4 show that the ratio of PBT to PET has a large influence on the material properties. The molecular structure unit of PET is less than that of PBT by two flexible methylene groups, so that the molecular chain has weak movement capability and strong rigidity and deformation resistance. The blending of PET and PBT is beneficial to reducing the material cost, and in addition, the excellent performances of the PET and PBT can be combined to make up for the defect of single component performance. However, when the addition amount of PET is too high, the bending property and unnotched impact strength of the composite material are obviously reduced, and the thermal conductivity of the composite material is reduced because the thermal conductivity of PET is lower than that of PBT.
Examples 1 and 3 and comparative example 5 show that the toughening agent has obvious toughening effect on the material and improves unnotched impact strength, but the loss of bending property of the material is caused by too much addition amount because the strength and modulus of the toughening agent are lower.
Examples 1, 4-7 and comparative examples 1-3 show that graphene-Fe prepared according to the present invention3O4The composite filler has good dispersibility in a PBT/PET matrix, part of small-radius graphene is filled in the fracture of the large-radius graphene heat conduction connection, the electric and heat conduction network structure can be effectively formed by low addition amount, and compared with the simple mixing of the single large-radius graphene filler and three fillers, the thermal conductivity and the electromagnetic shielding effectiveness are obviously improved. The good dispersion of the filler in the matrix avoids local stress concentration, and meanwhile, the small-radius graphene covers the large-radius graphene, so that the stress distribution is changed, cracks are expanded on the interface of the filler and the polymer, and finally, the energy is dispersed on the surface of the large-radius graphene sheet layer and the small-radius graphene sheet layer, and the mechanical property of the material is improved.
Example 1 and comparative example 6 show that the composite material prepared by adding the filler surface treating agent has better mechanical property, thermal conductivity and electromagnetic shielding effectiveness, because the graphene-Fe is improved after the filler surface treating agent is treated3O4The surface tension of the composite filler is beneficial to wetting and unfolding of a polymer on the surface of the filler, and the dispersibility of the filler in a PBT/PET matrix and the compatibility of the filler and the matrix are improved.
The above embodiments are merely illustrative of the technical solutions of the present invention and not restrictive, and it should be understood that various changes, modifications, substitutions and alterations can be made herein without departing from the principle and spirit of the invention as defined by the appended claims and their equivalents.

Claims (9)

1. The PBT/PET nanocomposite material with high electromagnetic shielding and heat conduction is characterized by comprising the following components in parts by weight: 70-80 parts of polybutylene terephthalate, 20-30 parts of polyethylene terephthalate, 5-10 parts of toughening agent and graphene-Fe3O45-10 parts of composite filler, 0.05-1 part of filler surface treating agent and 0.5-1.4 parts of antioxidant; the graphene-Fe3O4The composite filler is prepared by the following method:
(1) adding large-sheet-diameter graphene nanoplatelets, small-sheet-diameter graphene nanoplatelets and sodium dodecyl benzene sulfonate into deionized water, and ultrasonically dispersing for 3-5 hours to prepare a graphene dispersion liquid; the mass ratio of the large-sheet-diameter graphene nanoplatelets to the small-sheet-diameter graphene nanoplatelets to the sodium dodecyl benzene sulfonate to the deionized water is 2-3:1:1.5-4: 300-.
(2) Adding ferric chloride hexahydrate and ferrous chloride tetrahydrate into deionized water to prepare a ferrous salt/ferric salt solution, wherein the mass ratio of the ferric chloride hexahydrate to the ferrous chloride tetrahydrate to the deionized water is 1-2:1: 40-60.
(3) Adding a ferrous salt/ferric salt solution into the graphene dispersion liquid, ultrasonically dispersing for 1-2h, adding ammonia water at the stirring speed of 700rpm under the protection of nitrogen to adjust the pH value to about 8-10, heating to 40-60 ℃, and reacting for about 1-2h, wherein the mass ratio of the ferrous salt/ferric salt solution to the graphene dispersion liquid is 1.7-2.6: 1.
(4) Cooling to room temperature after the reaction is finished, performing suction filtration, washing a filter cake to be neutral by using ethanol and deionized water, and drying at 70-90 ℃ for 6h to obtain graphene-Fe3O4And (4) composite filling.
2. The PBT/PET nanocomposite material with high electromagnetic shielding and heat conduction of claim 1, wherein the graphene nanoplatelets with large sheet diameters have a thickness of about 5 to 100nm and a particle size D5090.0-130.0 μm, and more than 10 layers.
3. The PBT/PET nanocomposite material with high electromagnetic shielding and heat conduction as claimed in claim 1, wherein the PBT/PET nanocomposite material,the thickness of the small-particle-diameter graphene nanoplatelets is about 5-100nm, and the particle size D5010.0-14.0 μm, and more than 10 layers.
4. The PBT/PET nanocomposite material with high electromagnetic shielding and heat conduction as claimed in claim 1, wherein the toughening agent is prepared by mixing one or more of glycidyl methacrylate grafted ethylene-octene copolymer, maleic anhydride grafted styrene-ethylene-butene-styrene copolymer, methyl acrylate-butadiene-styrene copolymer and ethylene-methyl acrylate-glycidyl methacrylate copolymer according to any proportion.
5. The PBT/PET nanocomposite material with high electromagnetic shielding and heat conduction as claimed in claim 1, wherein the filler surface treatment agent is prepared by mixing one or more of a silane coupling agent KH560, a silane coupling agent KH550, a titanate coupling agent and methyl silicone oil according to any proportion.
6. The high-strength electromagnetic shielding and heat conducting PBT/PET nanocomposite material as claimed in claim 1, wherein the antioxidant is prepared by mixing one or two of an antioxidant 1010 and an antioxidant 168 according to any proportion.
7. The PBT/PET nanocomposite material with high electromagnetic shielding and heat conduction as claimed in claim 1, wherein the filler surface treatment agent is graphene-Fe3O4The mass ratio of the composite filler is 1-10: 100.
8. A preparation method of the high electromagnetic shielding and heat conducting PBT/PET nano composite material as claimed in claim 1, characterized by comprising the following steps:
(1) mixing graphene-Fe3O4The composite filler and the filler surface treating agent are uniformly mixed in a high-speed mixer.
(2) And (3) melting, blending and extruding the treated filler, polybutylene terephthalate, polyethylene terephthalate, toughening agent and antioxidant by using a double-screw extruder for granulation to obtain the high-strength electromagnetic shielding and heat-conducting PBT/PET nanocomposite material.
9. The preparation method of the PBT/PET nanocomposite material with high electromagnetic shielding and heat conduction as claimed in claim 8, wherein in the step (2), the temperature of the barrel of the twin-screw extruder is 240-260 ℃, and the rotation speed of the screw is 250-350 rpm.
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