CN115339112B - Three-dimensional high-heat-conductivity electromagnetic shielding polyaryletherketone composite material and preparation method and application thereof - Google Patents
Three-dimensional high-heat-conductivity electromagnetic shielding polyaryletherketone composite material and preparation method and application thereof Download PDFInfo
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- 238000002360 preparation method Methods 0.000 title claims abstract description 23
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- VCCBEIPGXKNHFW-UHFFFAOYSA-N biphenyl-4,4'-diol Chemical compound C1=CC(O)=CC=C1C1=CC=C(O)C=C1 VCCBEIPGXKNHFW-UHFFFAOYSA-N 0.000 description 4
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- ZCILODAAHLISPY-UHFFFAOYSA-N biphenyl ether Natural products C1=C(CC=C)C(O)=CC(OC=2C(=CC(CC=C)=CC=2)O)=C1 ZCILODAAHLISPY-UHFFFAOYSA-N 0.000 description 3
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- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
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- KZTYYGOKRVBIMI-UHFFFAOYSA-N diphenyl sulfone Chemical compound C=1C=CC=CC=1S(=O)(=O)C1=CC=CC=C1 KZTYYGOKRVBIMI-UHFFFAOYSA-N 0.000 description 2
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- DPXJVFZANSGRMM-UHFFFAOYSA-N acetic acid;2,3,4,5,6-pentahydroxyhexanal;sodium Chemical compound [Na].CC(O)=O.OCC(O)C(O)C(O)C(O)C=O DPXJVFZANSGRMM-UHFFFAOYSA-N 0.000 description 1
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- 125000003118 aryl group Chemical group 0.000 description 1
- 230000002238 attenuated effect Effects 0.000 description 1
- FJDQFPXHSGXQBY-UHFFFAOYSA-L caesium carbonate Chemical compound [Cs+].[Cs+].[O-]C([O-])=O FJDQFPXHSGXQBY-UHFFFAOYSA-L 0.000 description 1
- 229910000024 caesium carbonate Inorganic materials 0.000 description 1
- CREMABGTGYGIQB-UHFFFAOYSA-N carbon carbon Chemical compound C.C CREMABGTGYGIQB-UHFFFAOYSA-N 0.000 description 1
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Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C65/00—Joining or sealing of preformed parts, e.g. welding of plastics materials; Apparatus therefor
- B29C65/02—Joining or sealing of preformed parts, e.g. welding of plastics materials; Apparatus therefor by heating, with or without pressure
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C66/00—General aspects of processes or apparatus for joining preformed parts
- B29C66/40—General aspects of joining substantially flat articles, e.g. plates, sheets or web-like materials; Making flat seams in tubular or hollow articles; Joining single elements to substantially flat surfaces
- B29C66/41—Joining substantially flat articles ; Making flat seams in tubular or hollow articles
-
- 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
Landscapes
- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Physics & Mathematics (AREA)
- Electromagnetism (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention provides a three-dimensional high-heat-conductivity electromagnetic shielding polyaryletherketone composite material and a preparation method and application thereof, and belongs to the technical field of composite materials. The invention provides a polyarylether composite fiber membrane, which comprises a polyarylether matrix and first carbon-based fillers which are directionally arranged and dispersed in the polyarylether matrix; providing a polyether-ether-ketone composite microsphere, wherein the polyether-ether-ketone composite microsphere comprises a polyether-ether-ketone matrix and second carbon-based fillers which are directionally arranged and dispersed in the polyether-ether-ketone matrix; cold press molding is carried out on the polyether-ether-ketone composite microsphere to obtain a polyether-ether-ketone composite sheet; and placing at least one layer of polyether-ether-ketone composite sheet and at least one layer of polyarylether composite fiber film in a lamination way, and performing hot press molding to obtain the three-dimensional high-heat-conductivity electromagnetic shielding polyarylether-ketone composite material. The invention combines the polyarylether composite fiber membrane with the filler having orientation degree and the polyether-ether-ketone composite sheet, so that the obtained polyarylether-ketone composite material has good heat conduction and electromagnetic shielding performance.
Description
Technical Field
The invention relates to the technical field of composite materials, in particular to a three-dimensional high-heat-conductivity electromagnetic shielding polyaryletherketone composite material, and a preparation method and application thereof.
Background
With the continuous update of electronic technology and the development of intelligence, integration and miniaturization, electronic and electric products are gradually penetrated and interconnected to more industries, and thus the heat dissipation problem of the products is increasingly aggravated. The development of thermally conductive materials is particularly important because high-speed or full-speed operation of electronic chips and devices can generate significant amounts of heat, which can reduce device efficiency and lifetime if not dissipated in time. At present, composite materials with heat conduction and electromagnetic shielding performances are often required in the fields of electronic partition packaging, communication base stations, military aviation and the like, and along with the development requirement of light weight of materials, functionalized polymer-based composite materials are promoted to rapidly develop and are widely applied. In addition, under severe conditions of high temperature and high strength, such as application scenarios like spacecraft and military reconnaissance equipment, high performance polymer-based thermally conductive electromagnetic shielding composites are often required. Thus, high performance polymer-based thermally conductive electromagnetic shielding composites have attracted attention from many researchers.
The polyaryletherketone is a thermoplastic special engineering resin, has very excellent thermal stability and mechanical property, is widely applied to the fields of medical treatment, separation, machinery, aerospace, petrochemical industry and the like, and can be used as a matrix of a high-performance polymer matrix composite material. Researches show that by adding the filler and improving the orientation degree of the filler arrangement, a good heat conduction path or network is constructed, and the heat conduction and electromagnetic shielding performance of the polymer matrix composite can be improved. Chinese patent CN114316573a discloses a method for preparing an oriented ordered three-dimensional communication network electric conduction and heat conduction structure based on slurry, specifically, slurry including functional filler, water-based polymer resin and solvent water is prepared by freeze drying technology to obtain the oriented ordered three-dimensional communication network electric conduction and heat conduction structure. Chinese patent CN111978732B provides a method for preparing a thermal interface material with a three-dimensional heat conducting network structure, wherein the composite filler is arranged in a liquid resin in a directional manner by a magnetic field or an extrusion method, and the thermal interface material is obtained by cutting the composite filler along the direction of the directional arrangement by an ultrasonic knife after solidification. However, most of high-performance thermoplastic polyaryletherketone resins have poor dissolution capacity and high melt processing temperature, and the method has low applicability for enhancing the heat conduction and electromagnetic shielding performance of the thermoplastic polyaryletherketone composite material.
Disclosure of Invention
The invention aims to provide a three-dimensional high-heat-conductivity electromagnetic shielding polyaryletherketone composite material, a preparation method and application thereof.
In order to achieve the above object, the present invention provides the following technical solutions:
The invention provides a preparation method of a three-dimensional high-heat-conductivity electromagnetic shielding polyaryletherketone composite material, which comprises the following steps:
providing a polyarylether composite fiber membrane, wherein the polyarylether composite fiber membrane comprises a polyarylether matrix and first carbon-based fillers which are directionally arranged and dispersed in the polyarylether matrix;
providing a polyether-ether-ketone composite microsphere, wherein the polyether-ether-ketone composite microsphere comprises a polyether-ether-ketone matrix and second carbon-based fillers which are directionally arranged and dispersed in the polyether-ether-ketone matrix;
Cold press molding is carried out on the polyether-ether-ketone composite microsphere to obtain a polyether-ether-ketone composite sheet;
and placing at least one layer of polyether-ether-ketone composite sheet and at least one layer of polyarylether composite fiber film in a lamination way, and then performing hot press molding to obtain the three-dimensional high-heat-conductivity electromagnetic shielding polyarylether-ketone composite material.
Preferably, the first carbon-based filler comprises a carbon nanotube material and a graphene nanoplatelet material, and the mass ratio of the carbon nanotube material to the graphene nanoplatelet material is (5-9): (1-5);
The second carbon-based filler comprises 6-10 parts of carbon nano tube material and 0-4 parts of graphene nano sheet material in parts by mass;
The carbon nano tube materials in the first carbon-based filler and the second carbon-based filler are independently unfunctionalized carbon nano tubes or functionalized carbon nano tubes, and the graphene nano sheet materials are independently unfunctionalized graphene nano sheets or functionalized graphene nano sheets; the functionalization modes in the functionalized carbon nanotubes and the functionalized graphene nanoplatelets are independently amino functionalization, carboxyl functionalization or hydroxyl functionalization.
Preferably, the polyarylether composite fiber membrane is prepared from spinning solution comprising polyaryletherketone imine and a first carbon-based filler through electrostatic spinning; the content of the first carbon-based filler in the polyarylether composite fiber film is less than or equal to 30 weight percent.
Preferably, the polyether-ether-ketone composite microsphere is prepared by sequentially pre-cooling mixed dispersion liquid comprising polyether-ether-ketone, a second carbon filler and a water-based polymer by liquid nitrogen and freeze-drying; the content of the second carbon-based filler in the polyether-ether-ketone composite microsphere is less than or equal to 30 weight percent.
Preferably, the preparation method of the polyether-ether-ketone composite sheet comprises the following steps:
paving a part of polyether-ether-ketone composite microspheres in a single layer, and then performing first cold press molding to obtain a netlike sheet precursor;
and paving the residual polyether-ether-ketone composite microspheres at the non-connection point of the mesh sheet precursor for second cold press molding to obtain the polyether-ether-ketone composite sheet.
Preferably, the mass ratio of the partial polyether-ether-ketone composite microsphere to the residual polyether-ether-ketone composite microsphere is 1: (0.3-1.5).
Preferably, the pressure of the first cold press molding is 5-15 MPa, and the dwell time is 5-15 min; the pressure of the second cold press molding is 5-35 MPa, and the pressure maintaining time is 5-20 min.
Preferably, the temperature of the hot press molding is 360-390 ℃, the pressure is 10-35 MPa, and the heat preservation and pressure maintaining time is 5-20 min.
The invention provides the three-dimensional high-heat-conductivity electromagnetic shielding polyaryletherketone composite material prepared by the preparation method.
The invention provides application of the three-dimensional high-heat-conductivity electromagnetic shielding polyaryletherketone composite material in aerospace, electronic and electric industries, mechanical industries or military.
The invention provides a preparation method of a three-dimensional high-heat-conductivity electromagnetic shielding polyaryletherketone composite material, which comprises the following steps: providing a polyarylether composite fiber membrane, wherein the polyarylether composite fiber membrane comprises a polyarylether matrix and first carbon-based fillers which are directionally arranged and dispersed in the polyarylether matrix; providing a polyether-ether-ketone composite microsphere, wherein the polyether-ether-ketone composite microsphere comprises a polyether-ether-ketone matrix and second carbon-based fillers which are directionally arranged and dispersed in the polyether-ether-ketone matrix; cold press molding is carried out on the polyether-ether-ketone composite microsphere to obtain a polyether-ether-ketone composite sheet; and placing at least one layer of polyether-ether-ketone composite sheet and at least one layer of polyarylether composite fiber film in a lamination way, and then performing hot press molding to obtain the three-dimensional high-heat-conductivity electromagnetic shielding polyarylether-ketone composite material. According to the invention, the polyarylether composite fiber membrane with the orientation degree of the filler and the polyether-ether-ketone composite sheet are compounded, so that a good three-dimensional interconnected filler transmission network is constructed, efficient and stable transmission of phonons and electrons is facilitated, the scattering of phonons is reduced, heat can be dissipated in time, and electromagnetic waves are attenuated rapidly. In addition, the filler has the synergistic effect of two polymer composite materials with orientation degree, so that the anisotropy of the heat conducting property of the polymer composite materials is weakened, the excellent heat conducting enhancement property is obtained in the horizontal direction, the heat conducting property in the vertical direction is improved, meanwhile, the problem of interface scattering caused by phonon mismatch between the polymer and the filler can be solved, and the polyaryletherketone composite material is guaranteed to have good heat conducting and electromagnetic shielding properties.
Further, the carbon-based filler adopted in the invention comprises a one-dimensional carbon nano tube material and a two-dimensional graphene nano sheet material, the two materials are matched to use, so that the contact area between the fillers is increased, the perfection of a heat conduction path is further promoted, a three-dimensional filler network formed by the two materials and connected with each other provides a channel for high-speed transmission of phonons, the two effects are beneficial to reducing the interface thermal resistance of the composite material, and the scattering effect caused by phonon mismatch effect at the interface is reduced, so that the heat conduction performance of the composite material is effectively improved; meanwhile, the good three-dimensional filler network is also very beneficial to enhancing the shielding performance of the composite material on electromagnetic waves.
Drawings
FIG. 1 is a schematic diagram of the principle of heat conduction and electromagnetic shielding performance enhancement of a polyaryletherketone composite material in the invention;
FIG. 2 is a graph showing the thermal weight loss of the polyaryletherketone composite of example 1;
FIG. 3 is a scanning electron microscope image of the polyaryletherketone composite material of example 3;
FIG. 4 is a graph showing electromagnetic shielding performance of the polyaryletherketone composite material of example 4.
Detailed Description
The invention provides a preparation method of a three-dimensional high-heat-conductivity electromagnetic shielding polyaryletherketone composite material, which comprises the following steps:
providing a polyarylether composite fiber membrane, wherein the polyarylether composite fiber membrane comprises a polyarylether matrix and first carbon-based fillers which are directionally arranged and dispersed in the polyarylether matrix;
providing a polyether-ether-ketone composite microsphere, wherein the polyether-ether-ketone composite microsphere comprises a polyether-ether-ketone matrix and second carbon-based fillers which are directionally arranged and dispersed in the polyether-ether-ketone matrix;
Cold press molding is carried out on the polyether-ether-ketone composite microsphere to obtain a polyether-ether-ketone composite sheet;
and placing at least one layer of polyether-ether-ketone composite sheet and at least one layer of polyarylether composite fiber film in a lamination way, and then performing hot press molding to obtain the three-dimensional high-heat-conductivity electromagnetic shielding polyarylether-ketone composite material.
In the present invention, the raw materials used are commercially available products well known to those skilled in the art unless specified otherwise.
The invention provides a polyarylether composite fiber membrane, which comprises a polyarylether matrix and first carbon-based fillers which are directionally arranged and dispersed in the polyarylether matrix. In the present invention, the first carbon-based filler preferably includes a carbon nanotube material and a graphene nanoplatelet material, and the mass ratio of the carbon nanotube material to the graphene nanoplatelet material is preferably (5 to 9): (1 to 5), more preferably (6 to 9): (1 to 4), more preferably (7 to 8): (2-3). In the present invention, the length of the carbon nanotube material in the first carbon-based filler is preferably 5 to 15 μm, and the aspect ratio is preferably (35 to 250): 1, a step of; the carbon nanotube material is preferably a single-walled carbon nanotube material or a multi-walled carbon nanotube material. In the present invention, the thickness (i.e., longitudinal dimension) of the graphene nanoplatelets in the first carbon-based filler is preferably 1 to 20nm, and the sheet diameter (i.e., transverse dimension) is preferably 1 to 20 μm. In the invention, the carbon nanotube material in the first carbon-based filler is specifically an unfunctionalized carbon nanotube or a functionalized carbon nanotube, and the graphene nanosheet material is specifically an unfunctionalized graphene nanosheet or a functionalized graphene nanosheet; the way of functionalization in the functionalized carbon nanotubes and functionalized graphene nanoplatelets is independently preferably amino-functionalized, carboxyl-functionalized or hydroxyl-functionalized. In the present invention, the functionalized carbon nanotubes and functionalized graphene nanoplatelets are preferably commercially available as known to those skilled in the art; wherein, when the functionalization mode of the functionalized graphene nano-sheet is amino functionalization, the functionalized graphene nano-sheet is denoted as an amino graphene nano-sheet, the preparation method of the amino graphene nano-sheet preferably comprises the following steps:
mixing 4,4' -oxydiphenylamine, concentrated acid and sodium nitrite solution, and carrying out diazotization reaction to obtain a first product system; the concentrated acid is concentrated hydrochloric acid or concentrated sulfuric acid;
mixing the first product system with graphene nano sheet dispersion liquid, and performing grafting reaction to obtain a second product system;
and mixing the second product system with triethylamine, and carrying out neutralization reaction to obtain the amino graphene nano-sheet.
The invention mixes 4,4' -oxydiphenylamine, concentrated acid and sodium nitrite solution to carry out diazotization reaction to obtain a first product system. In the invention, the concentrated acid is concentrated hydrochloric acid or concentrated sulfuric acid; the concentration of the concentrated hydrochloric acid is preferably 11.8-13 mol/L, more preferably 12-12.5 mol/L, and the concentration of the concentrated sulfuric acid is preferably 9-12 mol/L, more preferably 9.5-11 mol/L; the molar ratio of the concentrated acid to the 4,4' -oxydiphenylamine is preferably (1.5-5): 1, more preferably (2 to 4): 1, more preferably (2.5 to 3): 1, wherein the amount of the substance of concentrated hydrochloric acid is calculated as HCl and the amount of the substance of concentrated sulfuric acid is calculated as H 2SO4. In the present invention, the molar ratio of the 4,4' -oxydiphenylamine to sodium nitrite in the sodium nitrite solution is preferably 1: (2 to 7), more preferably 1: (2 to 5), more preferably 1: (2.5-3); the concentration of the sodium nitrite solution is preferably 1 to 1.5mol/L, more preferably 1.1 to 1.3mol/L. In the present invention, the 4,4' -oxydiphenylamine, a concentrated acid and a sodium nitrite solution are mixed, preferably, 4' -oxydiphenylamine is added to the concentrated acid, the resulting 4,4' -oxydiphenylamine solution is cooled to 3 to 5 ℃, and then the sodium nitrite solution is added dropwise under stirring. In the present invention, the temperature of the diazotization reaction is preferably 0 to 15 ℃, more preferably 5 to 12 ℃, still more preferably 8 to 10 ℃; the time is preferably 30 to 60 minutes, more preferably 30 to 45 minutes; the diazotisation reaction is preferably carried out under stirring. In the invention, in the process of the azide reaction, the amino group of the 4,4' -oxydiphenylamine generates diazonium salt and amine salt respectively to obtain a tan biphenyl ether solution containing the diazonium salt and the amine salt, namely a first product system.
After the first product system is obtained, the first product system is mixed with the graphene nano sheet dispersion liquid, and grafting reaction is carried out, so that a second product system is obtained. In the present invention, the molar ratio of the 4,4' -oxydiphenylamine to the graphene nanoplatelets in the graphene nanoplatelet dispersion is preferably (1 to 3): 1, more preferably (1.25 to 2.5): 1, more preferably (1.5 to 2): 1. in the present invention, the concentration of the graphene nanoplatelet dispersion is preferably 1 to 5mg/mL, more preferably 1.5 to 4mg/mL, still more preferably 2 to 3mg/mL; the solvent of the graphene nano sheet dispersion liquid is preferably an organic solvent and water, and the volume ratio of the organic solvent to the water is preferably (1-5): 1, more preferably (2 to 3.5): 1, a step of; the organic solvent is preferably one or more of N, N-dimethylformamide, N-dimethylacetamide and N-methylpyrrolidone. In the present invention, the graphene nanoplatelets preferably have a thickness (i.e., longitudinal dimension) of 1 to 20nm and a sheet diameter (i.e., transverse dimension) of 1 to 20 μm. According to the invention, the graphene nano-sheets are dispersed in a mixture of an organic solvent and water under an ultrasonic condition to obtain graphene nano-sheet dispersion liquid. In the present invention, the mixing of the first product system with the graphene nanoplatelet dispersion preferably adds the first product system to the graphene nanoplatelet dispersion. In the present invention, the temperature of the grafting reaction is preferably 60 to 90 ℃, more preferably 70 to 85 ℃, still more preferably 75 to 80 ℃; the time is preferably 5 to 20 hours, more preferably 10 to 16 hours, still more preferably 12 to 14 hours. In the invention, in the grafting reaction process, diazonium salt contained in the first product system generates free radicals after electron denitrification, and then generates addition reaction with carbon-carbon double bonds on the graphene nano-sheets to generate new carbon-carbon single bonds and are connected through the covalent bonds.
After a second product system is obtained, the second product system is mixed with triethylamine, and neutralization reaction is carried out, so that the amino graphene nano-sheet is obtained. In the present invention, the molar ratio of 4,4' -oxydiphenylamine to triethylamine is preferably 1: (1 to 3), more preferably 1: (1.5 to 2.5), more preferably 1: (2-2.3). In the present invention, the second product system is mixed with triethylamine, preferably triethylamine is added to the second product system. In the present invention, the temperature of the neutralization reaction is preferably 30 to 60 ℃, more preferably 40 to 50 ℃; the time is preferably 30 to 90 minutes, more preferably 40 to 60 minutes; the neutralization reaction is preferably carried out under stirring. In the invention, during the neutralization reaction, the aromatic salt compound (namely, ammonium salt generated during the azide reaction) on the graphene nanoplatelets obtained after the grafting reaction is converted into aromatic amine through triethylamine neutralization.
After the neutralization reaction, the invention preferably carries out solid-liquid separation on the obtained product system, and washes and dries the obtained solid materials in sequence to obtain the amino graphene nano-sheets. In the present invention, the solid-liquid separation is preferably filtration, more preferably filtration using a vacuum pump; the washing preferably comprises washing with an organic solvent and washing with water sequentially, and the optional species of the organic solvent is preferably the same as the solvent in the graphene nanoplatelet dispersion, and is not described herein. The drying method is not particularly limited, and the material can be sufficiently dried.
In the invention, the content of the first carbon-based filler in the polyarylether composite fiber film is preferably not more than 30wt%, and specifically may be 1wt%, 6wt%, 12wt%, 18wt%, 24wt% or 30wt%. In the present invention, the thickness of the polyarylether composite fiber film is preferably 50 to 200. Mu.m. In the present invention, the polyarylether composite fiber membrane is preferably prepared by electrospinning a spinning solution comprising a polyaryletherketone imine and a first carbon-based filler, and is described in detail below. In the invention, the preparation method of the polyarylether composite fiber membrane preferably comprises the following steps:
Mixing aniline, 4 '-difluorobenzophenone and toluene with a molecular sieve to perform substitution reaction to obtain N-phenyl (4, 4' -difluorodiphenyl) ketimine; mixing the N-phenyl (4, 4' -difluoro diphenyl) ketimine, a phenolic compound, a catalyst, an organic solvent and a water-carrying agent, and carrying out polymerization reaction to obtain polyaryletherketone imine; the phenolic compound is hydroquinone or 4,4' -biphenol;
Mixing the polyaryletherketone imine, the first carbon-based filler and an organic solvent to obtain spinning solution;
and carrying out electrostatic spinning on the spinning solution to obtain the polyarylether composite fiber membrane.
The invention mixes aniline, 4 '-difluorobenzophenone, toluene and molecular sieve to carry out substitution reaction, and obtains N-phenyl (4, 4' -difluorodiphenyl) ketimine. In the present invention, the molar ratio of 4,4' -difluorobenzophenone to aniline is preferably 1: (1 to 1.5), more preferably 1: (1.1 to 1.5), more preferably 1: (1.3-1.5). In the invention, the toluene is used as a solvent, and the molecular sieve has the functions of removing water and preventing bumping in the toluene, and the dosage of the water and the bumping can meet the requirement that the substitution reaction is smoothly carried out, and the invention is not limited in particular. In the present invention, the substitution reaction is preferably carried out under reflux conditions; the time of the substitution reaction is preferably 6 to 48 hours, more preferably 20 to 24 hours; the substitution reaction is preferably carried out in a protective atmosphere, and the kind of the protective gas for providing the protective atmosphere is not particularly limited, and may be specifically nitrogen; the substitution reaction is preferably carried out under stirring. After the substitution reaction, the obtained product is preferably subjected to solid-liquid separation to remove the molecular sieve, the obtained filtrate is evaporated to remove the solvent, and the obtained crude product is recrystallized in methanol to obtain N-phenyl (4, 4' -difluoro diphenyl) ketimine as yellow crystals.
After obtaining N-phenyl (4, 4 '-difluoro diphenyl) ketimine, the invention mixes the N-phenyl (4, 4' -difluoro diphenyl) ketimine, phenolic compound, catalyst, organic solvent and water-carrying agent for polymerization reaction to obtain polyaryletherketone imine. In the invention, the phenolic compound is hydroquinone or 4,4 '-biphenol, specifically, hydroquinone is adopted as a raw material, the final preparation is benzene-side-group-containing polyether-ether-ketone imine, and 4,4' -biphenol is adopted as a raw material, so that the final preparation is benzene-side-group-containing biphenyl-type polyether-ether-ketone imine. In the present invention, the molar ratio of the N-phenyl (4, 4' -difluorodiphenyl) ketimine to the phenolic compound is preferably (1.5 to 1): 1, more preferably (1.2 to 1): 1. in the present invention, the catalyst preferably includes one or more of potassium carbonate, sodium carbonate, cesium carbonate, sodium bicarbonate and sodium hydroxide, and the molar ratio of the 4,4' -biphenol to the catalyst is preferably 1: (1.1 to 1.5), more preferably 1: (1.1 to 1.4), more preferably 1: (1.1-1.3). In the present invention, the organic solvent preferably includes one or more of diphenyl sulfone, sulfolane, dimethyl sulfoxide and N, N-dimethylacetamide; the water-carrying agent preferably comprises one or more of benzene, toluene and xylene; the volume ratio of the water-carrying agent to the organic solvent is preferably (0.1-0.7): 1, more preferably (0.4 to 0.7): 1, a step of; the specific amounts of the water-carrying agent and the organic solvent are preferably from 6 to 25% by weight, more preferably from 10 to 25% by weight, based on 5 to 30% by weight of the solid content of the system in which the polymerization reaction is carried out. In the present invention, the polymerization reaction is preferably preceded by a water removal treatment, the temperature of which is preferably 120 to 160 ℃, more preferably 130 to 140 ℃; the time of the water removal treatment is preferably 1 to5 hours, more preferably 2 to 3 hours; the water removal treatment is preferably carried out in a protective atmosphere. In the present invention, the temperature of the polymerization reaction is preferably 170 to 210 ℃, more preferably 180 to 190 ℃; the time is preferably 6 to48 hours, more preferably 8 to 12 hours; the polymerization is preferably carried out in a protective atmosphere; the substitution reaction is preferably carried out under stirring.
In the present invention, the polymerization reaction preferably further comprises: and discharging the obtained product system into methanol, and after solid-liquid separation, washing and drying the obtained solid material in sequence to obtain the aromatic polyether-ketone-imine. The solid-liquid separation mode is not particularly limited, and a mode well known to those skilled in the art, such as filtration, is adopted; the washing is preferably sequentially performed with water washing and ethanol washing, and the times of water washing and ethanol washing are independently preferably 2-5 times; the drying is preferably vacuum drying.
After obtaining the polyaryletherketone imine, the invention mixes the polyaryletherketone imine, the first carbon-based filler and the organic solvent to obtain the spinning solution. In the invention, the organic solvent preferably comprises one or more of tetrahydrofuran, dichloromethane, N-dimethylformamide, N-dimethylacetamide and N-methylpyrrolidone, and specifically can be a mixed solvent of N-methylpyrrolidone and tetrahydrofuran, or a mixed solvent of N-methylpyrrolidone and dichloromethane, or a mixed solvent of N, N-dimethylacetamide and tetrahydrofuran; the volume ratio of the N-methylpyrrolidone to the tetrahydrofuran in the mixed solvent of the N-methylpyrrolidone and the tetrahydrofuran is preferably (4-5): 1, the volume ratio of the N-methylpyrrolidone to the dichloromethane in the mixed solvent of the N-methylpyrrolidone and the dichloromethane is preferably (2-3): 1, the volume ratio of the N, N-dimethylacetamide to the dichloromethane in the mixed solvent of the N, N-dimethylacetamide and the dichloromethane is preferably (4-5): the volume ratio of the N, N-dimethylacetamide to the tetrahydrofuran in the mixed solvent of the N, N-dimethylacetamide and the tetrahydrofuran is preferably (4-5): 2; the amount of the organic solvent is preferably 10 to 16wt%, more preferably 11 to 14wt%, based on the total content of the polyaryletherketimine and the first carbon-based filler in the spinning solution of 7 to 20 wt%. Mixing polyaryletherketone imine, a first carbon-based filler and an organic solvent, and preferably sequentially stirring and ultrasonically oscillating to obtain spinning solution; the stirring is preferably magnetic stirring, and the stirring time is preferably 3-120 min, more preferably 60min; the time of the ultrasonic oscillation is preferably 10 to 60 minutes, more preferably 30 minutes.
After the spinning solution is obtained, the invention carries out electrostatic spinning on the spinning solution to obtain the polyarylether composite fiber membrane. In the present invention, the method of electrospinning the spinning solution preferably comprises: and placing the spinning solution in an injector, placing the injector containing the spinning solution in a propeller, then carrying out electrostatic spinning under the action of the propulsion of the propeller and an electric field, and collecting on a collecting plate to obtain the polyarylether composite fiber membrane. In the present invention, the conditions of the electrospinning include: the propulsion speed of the propeller is preferably 0.01-0.20 mL/min, more preferably 0.05-0.15 mL/min, still more preferably 0.06-0.09 mL/min, still more preferably 0.07-0.08 mL/min; during the propulsion, the propulsion speed of the propeller is preferably kept constant; the distance between the needle tip of the syringe and the collecting plate is preferably 5 to 20cm, more preferably 8 to 18cm, still more preferably 13 to 17cm, still more preferably 15 to 16cm; the voltage is preferably 5 to 25kV, more preferably 10 to 17kV, and even more preferably 15 to 16kV. In the invention, in the process of electrostatic spinning, the ambient temperature is preferably 20-25 ℃, more preferably 23 ℃; the relative humidity of air is preferably 10 to 40%, more preferably 25 to 30%. In an embodiment of the invention, the propeller is preferably an automatic propeller; the automatic propeller is preferably a conventional automatic propeller in the art.
After the electrostatic spinning, the obtained material is preferably dried to sufficiently remove the solvent; the drying temperature is preferably 100-120 ℃, more preferably 110-120 ℃; the time is preferably 6 to 48 hours, more preferably 6 to 10 hours.
The invention provides a polyether-ether-ketone composite microsphere, which comprises a polyether-ether-ketone matrix and second carbon-based fillers which are directionally arranged and dispersed in the polyether-ether-ketone matrix. In the invention, the second carbon-based filler preferably comprises 6-10 parts by weight of carbon nanotube material and 0-4 parts by weight of graphene nanoplatelet material; the carbon nanotube material is preferably 6 to 9 parts, more preferably 6.5 to 8 parts; the graphene nanoplatelet material is preferably 1 to 4 parts, more preferably 2 to 3.5 parts. In the present invention, the length of the carbon nanotube material in the second carbon-based filler is preferably 5 to 15 μm, and the aspect ratio is preferably (35 to 250): 1, a step of; the carbon nanotube material is preferably a single-walled carbon nanotube material or a multi-walled carbon nanotube material. In the present invention, the thickness (i.e., the longitudinal dimension) of the graphene nanoplatelets in the second carbon-based filler is preferably 1 to 20nm, and the sheet diameter (i.e., the transverse dimension) is preferably 1 to 20 μm. In the invention, the carbon nanotube material in the second carbon-based filler is specifically an unfunctionalized carbon nanotube or a functionalized carbon nanotube, and the graphene nanosheet material is specifically an unfunctionalized graphene nanosheet or a functionalized graphene nanosheet; the way of functionalization in the functionalized carbon nanotubes and functionalized graphene nanoplatelets is independently preferably amino-functionalized, carboxyl-functionalized or hydroxyl-functionalized. In the present invention, the source of the second carbon-based filler is preferably identical to that of the first carbon-based filler, and will not be described herein.
In the invention, the content of the second carbon-based filler in the polyether-ether-ketone composite microsphere is preferably less than or equal to 30wt%, and specifically can be 1wt%, 6wt%, 12wt%, 18wt%, 24wt% or 30wt%. In the invention, the content of the second carbon-based filler in the polyether-ether-ketone composite microsphere is preferably the same as the content of the first carbon-based filler in the polyarylether composite fiber membrane.
In the invention, the polyether-ether-ketone composite microsphere is prepared from a mixed dispersion liquid comprising polyether-ether-ketone, a second carbon-based filler and a water-based polymer through liquid nitrogen precooling and freeze drying in sequence, and is described in detail below. In the invention, the preparation method of the polyether-ether-ketone composite microsphere preferably comprises the following steps:
mixing a water-based polymer, a second carbon-based filler and polyether-ether-ketone powder with water to obtain a mixed dispersion liquid;
pre-freezing the mixed dispersion liquid in the form of liquid drops by adopting liquid nitrogen to obtain microsphere precursors;
and freeze-drying the microsphere precursor to obtain the polyether-ether-ketone composite microsphere.
The invention mixes the water polymer, the second carbon filler, the polyether-ether-ketone powder and water to obtain the mixed dispersion liquid. In the present invention, the aqueous polymer is preferably polyvinyl alcohol and/or sodium carboxymethyl cellulose; the surface of the water-based polymer is provided with a plurality of polar functional groups such as hydroxyl groups, the polar functional groups can be coated on the surfaces of the carbon nano tube and the functional heat-conducting filler in the material mixing process, and the ordered structure of the composite filler is formed in the subsequent pre-freezing and freeze-drying processes, so that the heat flow transmission in the composite material is facilitated, and the heat-conducting property is improved; and the interfacial compatibility between the composite filler and the polyether-ether-ketone can be improved, so that the interfacial thermal resistance of the composite material is reduced, and the heat conducting property is improved. In the present invention, the concentration of the aqueous polymer in the mixed dispersion is preferably 0.2 to 1.0wt%, more preferably 0.3 to 0.9wt%, and still more preferably 0.5 to 0.7wt%. The concentration of the aqueous polymer in the mixed dispersion is preferably limited to the above range, which is advantageous for forming an ordered structure in the composite filler during prefreezing and freeze-drying of the carbon nanotubes and the functionalized thermally conductive filler. In the present invention, the particle size of the polyether-ether-ketone powder is preferably 10 to 100. Mu.m. In the invention, the aqueous polymer, the second carbon-based filler and the polyether-ether-ketone powder are mixed with water, preferably the aqueous polymer is mixed with water to obtain an aqueous polymer solution; then adding a second carbon filler and polyether-ether-ketone powder, and stirring and ultrasonic oscillating sequentially. In the present invention, the stirring time is preferably 40 to 90 minutes, more preferably 60 minutes; the time of the ultrasonic oscillation is preferably 15 to 45 minutes, more preferably 30 minutes.
After the mixed dispersion liquid is obtained, the liquid nitrogen is adopted to pre-freeze the mixed dispersion liquid in the form of liquid drops, so as to obtain the microsphere precursor. In the present invention, the method of obtaining the mixed dispersion in the form of droplets preferably comprises: the mixed dispersion is placed in a propeller, and then extruded under the propulsion of the propeller to obtain liquid drops. In the present invention, the diameter of the droplet is preferably 500 to 1000. Mu.m. In the present invention, the propulsion speed of the propeller is preferably 0.1 to 2mL/min, more preferably 0.5 to 1.5mL/min, and still more preferably 0.7 to 0.8mL/min; the propeller is preferably an automatic propeller; the automatic propeller is preferably a conventional automatic propeller in the art. The invention preferably collects the liquid drops extruded from the propeller into a Dewar basin filled with liquid nitrogen for prefreezing to obtain microsphere precursors; the prefreezing temperature is preferably-80 to-30 ℃, more preferably-70 to-40 ℃, and further preferably-60 to-50 ℃; the time is preferably 0.5 to 3 hours, more preferably 2 to 3 hours. In the invention, in the pre-freezing process, the liquid drops are frozen into microspheres, and ice crystals in the microspheres slowly grow and drive the composite filler to be orderly arranged in the microsphere precursor.
After the microsphere precursor is obtained, the microsphere precursor is freeze-dried to obtain the polyether-ether-ketone composite microsphere. In the present invention, the temperature of the freeze-drying is preferably-55 to-35 ℃, more preferably-50 to-40 ℃, further preferably-45 to-42 ℃; the time is preferably 24 to 96 hours, more preferably 40 to 84 hours, and still more preferably 48 to 60 hours. The invention preferably carries out said lyophilization in a freeze-dryer. According to the invention, the moisture in the microsphere precursor is removed through freeze drying, specifically, in the freeze drying process, the orientation degree of the composite filler can be improved through the driving action of ice crystal growth, a relatively perfect three-dimensional heat conduction path or network is easier to construct, the heat flow is rapidly and stably conducted, the heat dissipation is facilitated, and a channel is provided for high-speed phonon transmission, so that the transmission efficiency of phonons and electrons can be effectively improved, the interface scattering of the phonons is reduced, and the interface thermal resistance is reduced.
After the polyether-ether-ketone composite microsphere is obtained, the polyether-ether-ketone composite microsphere is subjected to cold press molding to obtain the polyether-ether-ketone composite sheet. In the invention, the preparation method of the polyether-ether-ketone composite sheet preferably comprises the following steps:
paving a part of polyether-ether-ketone composite microspheres in a single layer, and then performing first cold press molding to obtain a netlike sheet precursor;
and paving the residual polyether-ether-ketone composite microspheres at the non-connection point of the mesh sheet precursor for second cold press molding to obtain the polyether-ether-ketone composite sheet.
According to the invention, after a part of polyether-ether-ketone composite microspheres are paved in a single layer, the first cold press molding is carried out, and a netlike sheet precursor is obtained. In the present invention, the pressure of the first cold press molding is preferably 5 to 15MPa, more preferably 6 to 12MPa, still more preferably 8 to 10MPa; the dwell time is preferably 5 to 15 minutes, more preferably 8 to 13 minutes, still more preferably 10 to 12 minutes. In the present invention, the first cold press molding is preferably performed under room temperature conditions.
After the mesh sheet precursor is obtained, the residual polyether-ether-ketone composite microspheres are paved at the non-connection point of the mesh sheet precursor for second cold press molding, so that the polyether-ether-ketone composite sheet is obtained. In the invention, the mass ratio of the partial polyether-ether-ketone composite microsphere to the residual polyether-ether-ketone composite microsphere is preferably 1: (0.3 to 1.5), more preferably 1: (0.5 to 1), more preferably 1: (0.8-0.9). In the invention, the non-connection point of the mesh-shaped sheet precursor is the mesh of the mesh-shaped sheet precursor. In the present invention, the pressure of the second cold press molding is preferably 5 to 35MPa, more preferably 10 to 30MPa, still more preferably 13 to 20MPa, still more preferably 15 to 18MPa; the dwell time is preferably 5 to 20 minutes, more preferably 8 to 20 minutes, still more preferably 10 to 12 minutes. In the present invention, the second cold press molding is preferably performed under room temperature conditions. The invention obtains the compact and complete polyether-ether-ketone composite sheet through the second cold press molding. In the invention, the thickness of the polyether-ether-ketone composite sheet is preferably 200-900 μm.
After the polyether-ether-ketone composite sheet and the polyarylether composite fiber membrane are obtained, at least one layer of the polyether-ether-ketone composite sheet and at least one layer of the polyarylether composite fiber membrane are placed in a lamination mode and then subjected to hot press forming, and the three-dimensional high-heat-conductivity electromagnetic shielding polyarylether-ketone composite material is obtained. In the invention, a plurality of groups of polyether-ether-ketone composite sheets and a plurality of groups of polyarylether composite fiber films are alternately stacked, wherein the number of layers of the polyether-ether-ketone composite sheets in each group of polyether-ether-ketone composite sheets is preferably 1, and the number of layers of the polyarylether composite fiber films in each group of polyarylether composite fiber films is preferably 1-4; the specific group numbers of the polyether-ether-ketone composite sheet and the polyarylether composite fiber membrane are determined according to actual needs, and specifically, the group number of the polyether-ether-ketone composite sheet is preferably 1-2, and the group number of the polyarylether composite fiber membrane is preferably 1-3. In the present invention, when the polyether-ether-ketone composite sheet and the polyarylether composite fiber film are stacked, the upper surface layer and the lower surface layer may be polyether-ether-ketone composite sheets or polyarylether composite fiber films, and the present invention is not particularly limited thereto.
In the present invention, the temperature of the hot press molding is preferably 360 to 390 ℃, more preferably 365 to 380 ℃, and even more preferably 370 to 375 ℃; the pressure is preferably 10 to 35MPa, more preferably 12 to 30MPa, still more preferably 15 to 28MPa; the holding time is preferably 5 to 20 minutes, more preferably 8 to 15 minutes, and still more preferably 10 to 12 minutes. In the present invention, the hot press molding is preferably further comprised of preheating, and the preheating temperature is preferably consistent with the hot press molding temperature, which is not described herein again; the preheating time is preferably 8 to 15 minutes, more preferably 10 to 12 minutes.
The invention provides the three-dimensional high-heat-conductivity electromagnetic shielding polyaryletherketone composite material prepared by the preparation method. According to the invention, the polyarylether composite fiber membrane with the orientation degree of the filler and the polyether-ether-ketone composite sheet are compounded, so that a good three-dimensional interconnected filler transmission network is constructed, the interface thermal resistance can be effectively reduced, the interface scattering of phonons is reduced, and the heat transfer efficiency is improved. In addition, the good three-dimensional filler network is also very favorable for enhancing the shielding performance of the composite material on electromagnetic waves, in particular, the good electric conduction performance can increase the impedance mismatch effect at the interface to improve the reflection loss of the composite material on electromagnetic waves, and the compact filler network in the composite material system can increase the reflection times of incident electromagnetic waves in the system to increase multiple reflection loss. Therefore, the polyaryletherketone composite material based on the three-dimensional filler network provided by the invention has excellent heat conduction and electromagnetic shielding performance.
The invention provides application of the three-dimensional high-heat-conductivity electromagnetic shielding polyaryletherketone composite material in aerospace, electronic and electric industries, mechanical industries or military.
FIG. 1 is a schematic diagram of the principle of heat conduction and electromagnetic shielding performance enhancement of a three-dimensional high-heat-conductivity electromagnetic shielding polyaryletherketone composite material, as shown in FIG. 1, for the heat conduction performance (TC), the composite material with the filler oriented arrangement obtained by the two methods is combined in a sandwich manner, so that a good filler network is formed, the rapid transmission of heat flow is facilitated, the interface thermal resistance is reduced, and the heat conduction capacity is improved; for electromagnetic shielding performance (EMI), the electromagnetic shielding performance of the composite material is improved by the formed good three-dimensional filler network, which is more beneficial to increasing the loss of electromagnetic waves.
The technical solutions of the present invention will be clearly and completely described in the following in connection with the embodiments of the present invention. It will be apparent that the described embodiments are only some, but not all, embodiments of the invention. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
The sources of some of the raw materials and index parameters used in the following examples and comparative examples are as follows:
The particle size of the polyether-ether-ketone superfine powder is 10-100 mu m;
The carbon nano tube is specifically an unfunctionalized multi-wall carbon nano tube, the length is 5-15 mu m, and the length-diameter ratio is (35-250): 1.
The diameter of the amino graphene nano sheet is 1-20 mu m, the thickness is 1-20 nm, and the preparation method comprises the following steps: 4,4 '-oxydiphenylamine (0.3 mmol) was mixed with concentrated sulfuric acid (9 mol/L,0.072 mL) to give a solution of 4,4' -oxydiphenylamine; cooling the 4,4' -oxydiphenylamine solution to 3-5 ℃, then dropwise adding the cooled 4,4' -oxydiphenylamine solution into a sodium nitrite aqueous solution (1.3 mol/L, the amount of sodium nitrite is 0.9 mmol) under the stirring condition, and continuously stirring the cooled 4,4' -oxydiphenylamine solution for 45min under the 15 ℃ condition after the addition to obtain a tan biphenyl ether solution containing azide salts and amine salts; mixing graphene nano sheets (0.125 mmol, sheet diameter size of 1-20 mu m and thickness of 1-20 nm) and N, N-dimethylacetamide with water under an ultrasonic condition to obtain graphene nano sheet dispersion liquid with concentration of 2.5mg/mL, wherein the volume ratio of the N, N-dimethylacetamide to the water is 2:1; adding the biphenyl ether solution into the graphene nano sheet dispersion liquid, and heating to 75 ℃ for reaction for 14h; and adding triethylamine (0.65 mmol) into the obtained product system after the reaction is finished, stirring and reacting for 60min at 40 ℃, filtering the obtained product system by a vacuum pump to obtain a crude product, sequentially adopting N, N-dimethylacetamide and water for washing, and drying to obtain the amino graphene nano-sheet.
Example 1
Adding 2g of filler (specifically carbon nano tube) into 100mL of 0.8wt% polyvinyl alcohol solution, uniformly dispersing by ultrasonic, then adding 31.33g of polyether-ether-ketone ultrafine powder, and uniformly stirring and dispersing to obtain mixed dispersion liquid; extracting the mixed dispersion liquid by using a syringe, extruding at a propulsion speed of 1.5mL/min by using an automatic propeller to obtain liquid drops (with a diameter of 200-800 mu m), collecting the liquid drops in Du Wapen filled with liquid nitrogen, pre-freezing for 3 hours at the temperature of-70 ℃, transferring the obtained microsphere precursor into a freeze dryer, and freeze-drying for 48 hours at the temperature of-50 ℃ to remove water, thereby obtaining the polyether-ether-ketone composite microsphere with the filler having an orientation arrangement structure, wherein the filler content is 6wt%.
4,4' -Difluorobenzophenone (0.1 mol), aniline (0.15 mol), toluene (80 mL) and molecular sieve (50 g) were added into a three-neck flask with a mechanical stirring device, a Dean-Stark trap and a condenser, heated to reflux under nitrogen protection, and stirred for 24 hours; cooling the obtained product system to room temperature, filtering to remove a molecular sieve, evaporating filtrate to remove a solvent, and recrystallizing the obtained crude product in methanol to obtain yellow crystal N-phenyl (4, 4' -difluoro diphenyl) ketimine; the N-phenyl (4, 4 '-difluorodiphenyl) ketimine (30 mmol), 4' -biphenol (30 mmol), anhydrous potassium carbonate (33 mmol), toluene (30 mL) and sulfolane (60 mL) are added into a three-neck flask with a mechanical stirring device, a Dean-Stark water separator and a condenser tube, and are heated to 160 ℃ under the protection of nitrogen to azeotropically remove water for 3h, and then the temperature is raised to 200 ℃, and the reaction is carried out under heat preservation and stirring for 6h; discharging the obtained product system into methanol, filtering, washing the obtained filter cake with water and ethanol for several times respectively, and then carrying out vacuum drying to obtain biphenyl type polyether-ether-ketone imine containing benzene side groups; adding 31.33g of biphenyl polyether-ether-ketone imine containing a benzene side group and 2g of filler (specifically, an aminated graphene nano sheet and a carbon nano tube with the mass ratio of 4:6) into a composite solvent (specifically, N-methylpyrrolidone and tetrahydrofuran with the volume ratio of 5:1), and carrying out ultrasonic oscillation for 30min to obtain a spinning solution with the total content of biphenyl polyether-ether-ketone imine containing a benzene side group and the filler of 15 wt%; extracting the spinning solution by using an injector, then placing the injector in an automatic propeller, and carrying out electrostatic spinning under the action of the propulsion of the propeller and an electric field, wherein the electrostatic spinning conditions comprise: the environment temperature is 25 ℃, the relative humidity of air is 30%, the propelling speed of a propeller is 0.05mL/min, the distance between the needle tip of the syringe and the collecting plate is 8cm, the voltage is 20kV (provided by a high-voltage power supply), the film material is finally collected on the collecting plate, and the film material is dried at 120 ℃ for 6 hours, so that the polyarylether composite fiber film (with the thickness of 30-150 mu m) with the filler having an orientation arrangement structure is obtained, and the filler content is 6wt%.
The polyether-ether-ketone composite microsphere single layer is fully paved in a die with the inner diameter of 6 multiplied by 6cm, then the die is placed in a die press, cold pressing is carried out for 12min under the condition of 8MPa to obtain a polyether-ether-ketone composite sheet precursor with a net structure, then the polyether-ether-ketone composite microsphere is paved at a non-connection point (namely a mesh point) of the polyether-ether-ketone composite sheet precursor, the paving amount of the polyether-ether-ketone composite microsphere is 50% of that of the first paving, and cold pressing is carried out for 12min under the condition of 10MPa to obtain a polyether-ether-ketone composite sheet with the thickness of 50-200 mu m; sequentially placing a polyarylether composite fiber film, a polyether-ether-ketone composite sheet and a polyarylether composite fiber film in another die with the inner diameter of 6 multiplied by 6cm, placing the die in a molding press, preheating for 12min at 365 ℃, then applying 30MPa pressure, preserving heat and pressure for 10min, cooling to room temperature, and demolding to obtain the polyarylether-ketone composite material.
Example 2
Polyether-ether-ketone composite microspheres were prepared according to the method of example 1, except that the content of the filler (specifically, carbon nanotubes) in the polyether-ether-ketone composite microspheres was 12wt%;
preparing a polyarylether composite fiber film according to the method of the embodiment 1, wherein the only difference is that the content of filler (specifically, the aminated graphene nano-sheets and the carbon nano-tubes in the mass ratio of 4:6) in the polyarylether composite fiber film is 12wt%;
The polyether-ether-ketone composite microsphere single layer is fully paved in a die with the inner diameter of 6 multiplied by 6cm, then the die is placed in a die press, cold pressing is carried out for 12min under the condition of 10MPa to obtain a polyether-ether-ketone composite sheet precursor with a net structure, then the polyether-ether-ketone composite microsphere is paved at a non-connection point (namely a mesh point) of the polyether-ether-ketone composite sheet precursor, the paving amount of the polyether-ether-ketone composite microsphere is 80% of that paved for the first time, and cold pressing is carried out for 10min under the condition of 13MPa to obtain a polyether-ether-ketone composite sheet with the thickness of 50-200 mu m; sequentially placing two polyarylether composite fiber films, one polyether-ether-ketone composite sheet and two polyarylether composite fiber films in another die with the inner diameter of 6 multiplied by 6cm, placing the die in a die press, preheating for 13min at 370 ℃, then applying 30MPa pressure, preserving heat and pressure for 12min, cooling to room temperature, and demoulding to obtain the polyarylether-ketone composite material.
Example 3
Polyether-ether-ketone composite microspheres were prepared according to the method of example 1, except that the content of the filler (specifically, carbon nanotubes) in the polyether-ether-ketone composite microspheres was 18wt%;
A polyarylether composite fiber film was prepared according to the method of example 1, except that the content of the filler (specifically, the aminated graphene nanoplatelets and the carbon nanotubes, the mass ratio of the aminated graphene nanoplatelets to the carbon nanotubes was 3:7) in the polyarylether composite fiber film was 18wt%;
The polyether-ether-ketone composite microsphere single layer is fully paved in a die with the inner diameter of 6 multiplied by 6cm, then the die is placed in a die press, cold pressing is carried out for 10min under the condition of 12MPa to obtain a polyether-ether-ketone composite sheet precursor with a net structure, then the polyether-ether-ketone composite microsphere is paved at a non-connection point (namely a mesh point) of the polyether-ether-ketone composite sheet precursor, the paving amount of the polyether-ether-ketone composite microsphere is 90% of that of the first paving, and cold pressing is carried out for 10min under the condition of 15MPa to obtain a polyether-ether-ketone composite sheet with the thickness of 50-200 mu m; and sequentially placing three polyarylether composite fiber films and one polyether-ether-ketone composite sheet in another die with the inner diameter of 6 multiplied by 6cm, placing the die in a molding press, preheating for 15min at 375 ℃, then applying 28MPa pressure, preserving heat and pressure for 10min, cooling to room temperature, and demolding to obtain the polyarylether-ketone composite material.
Example 4
Polyether-ether-ketone composite microspheres were prepared according to the method of example 1, except that the content of the filler (specifically, carbon nanotubes) in the polyether-ether-ketone composite microspheres was 24wt%;
A polyarylether composite fiber film was prepared according to the method of example 1, except that the content of the filler (specifically, the aminated graphene nanoplatelets and the carbon nanotubes, the mass ratio of which is 2:8) in the polyarylether composite fiber film was 24wt%;
The polyether-ether-ketone composite microsphere single layer is fully paved in a die with the inner diameter of 6 multiplied by 6cm, then the die is placed in a die press, cold pressing is carried out for 8min under the condition of 15MPa to obtain a polyether-ether-ketone composite sheet precursor with a net structure, then the polyether-ether-ketone composite microsphere is paved at a non-connection point (namely a mesh point) of the polyether-ether-ketone composite sheet precursor, the paving amount of the polyether-ether-ketone composite microsphere is 100 percent of that of the first paving (namely the paving amount of the two times is the same), and cold pressing is carried out for 10min under the condition of 18MPa to obtain the polyether-ether-ketone composite sheet with the thickness of 50-200 mu m; sequentially placing two polyarylether composite fiber films, one polyether-ether-ketone composite sheet and two polyarylether composite fiber films in another die with the inner diameter of 6 multiplied by 6cm, placing the die in a molding press, preheating for 15min at 375 ℃, then applying 30MPa pressure, preserving heat and pressure for 10min, cooling to room temperature, and demolding to obtain the polyarylether-ketone composite material.
Example 5
Polyether-ether-ketone composite microspheres were prepared according to the method of example 1, except that the content of the filler (specifically, carbon nanotubes) in the polyether-ether-ketone composite microspheres was 30wt%;
Preparing a polyarylether composite fiber film according to the method of the embodiment 1, wherein the content of (specifically, the aminated graphene nano-sheets and the carbon nano-tubes in the mass ratio of 3:7) in the polyarylether composite fiber film is 30wt%;
The polyether-ether-ketone composite microsphere single layer is fully paved in a die with the inner diameter of 6 multiplied by 6cm, then the die is placed in a die press, cold pressing is carried out for 8min under the condition of 15MPa to obtain a polyether-ether-ketone composite sheet precursor with a net structure, then the polyether-ether-ketone composite microsphere is paved at a non-connection point (namely a mesh point) of the polyether-ether-ketone composite sheet precursor, the paving amount of the polyether-ether-ketone composite microsphere is 100 percent of that of the first paving (namely the paving amount of the two times is the same), and cold pressing is carried out for 8min under the condition of 20MPa to obtain the polyether-ether-ketone composite sheet with the thickness of 50-200 mu m; sequentially placing three polyarylether composite fiber films, one polyether-ether-ketone composite sheet and three polyarylether composite fiber films in another die with the inner diameter of 6 multiplied by 6cm, then placing the die in a molding press, preheating for 15min at 380 ℃, then applying 30MPa pressure, preserving heat and pressure for 12min, cooling to room temperature, and demolding to obtain the polyarylether-ketone composite material.
Comparative example 1
Polyether-ether-ketone composite microspheres were prepared according to the method of example 1, except that the content of the filler in the polyether-ether-ketone composite microspheres was 30wt%;
Placing the polyether-ether-ketone composite microspheres in a die, and cold pressing for 8min under the condition of 15MPa to obtain a cold-pressed sheet; preheating for 25min at 380 ℃, then applying 25MPa pressure, preserving heat and pressure for 20min, cooling to room temperature, and demoulding to obtain the polyether-ether-ketone composite material.
Comparative example 2
A polyarylether composite fiber film was prepared according to the method of example 1, except that the content of the filler in the polyarylether composite fiber film was 30wt%;
And (3) placing the three polyarylether composite fiber films in a die, preheating for 25min in a hot press at 375 ℃, then applying 30MPa pressure, and preserving heat and pressure for 20min to obtain the polyarylether composite material.
Characterization and performance testing:
Fig. 2 is a thermal weight loss curve of the polyaryletherketone composite material in example 1, and as can be seen from fig. 2, the temperature of T 5 (weight loss 5%) is 505 ℃, the temperature of T 10 (weight loss 10%) is 532 ℃, which indicates that the polyaryletherketone composite material provided by the invention has excellent thermal stability.
Fig. 3 is a scanning electron microscope image of the polyaryletherketone composite material in example 3, and it is obvious from fig. 3 that an interlayer structure similar to a sandwich structure is observed, the polyaryletherketone composite fiber membranes on two sides are tightly combined with the polyether-ether-ketone composite sheet in the middle, and fillers with orientation degree in the two composite materials are mutually overlapped, that is, carbon nanotubes in the polyether-ether-ketone composite sheet in the middle and composite fillers (namely, aminated graphene nano sheets and carbon nanotubes) in the polyaryletherketone composite fiber membranes on two sides form more heat conduction paths, so that a good filler network is constructed, and the heat conduction performance and the electromagnetic wave shielding performance are improved.
Fig. 4 is a graph showing electromagnetic shielding performance of the polyaryletherketone composite material of example 4, and as can be seen from fig. 4, the polyaryletherketone composite material shows a shielding performance of 47dB at 12.4GHz when the total filler loading of the polyaryletherketone composite material is 24wt% and the thickness of the molded sheet is 230 μm.
The thermal conductivity of the composites prepared in the examples and comparative examples was measured using a flash LFA467 (germany) and the specific results are shown in table 1. As shown in Table 1, the polyaryletherketone composite material provided by the invention has excellent heat conduction performance.
Table 1 thermal conductivity of the composites prepared in examples and comparative examples
The foregoing is merely a preferred embodiment of the present invention and it should be noted that modifications and adaptations to those skilled in the art may be made without departing from the principles of the present invention, which are intended to be comprehended within the scope of the present invention.
Claims (9)
1. A preparation method of a three-dimensional high-heat-conductivity electromagnetic shielding polyaryletherketone composite material comprises the following steps:
providing a polyarylether composite fiber membrane, wherein the polyarylether composite fiber membrane comprises a polyarylether matrix and first carbon-based fillers which are directionally arranged and dispersed in the polyarylether matrix;
providing a polyether-ether-ketone composite microsphere, wherein the polyether-ether-ketone composite microsphere comprises a polyether-ether-ketone matrix and second carbon-based fillers which are directionally arranged and dispersed in the polyether-ether-ketone matrix;
Cold press molding is carried out on the polyether-ether-ketone composite microsphere to obtain a polyether-ether-ketone composite sheet;
placing at least one layer of polyether-ether-ketone composite sheet and at least one layer of polyarylether composite fiber film in a lamination way, and then performing hot press molding to obtain a three-dimensional high-heat-conductivity electromagnetic shielding polyarylether-ketone composite material;
The first carbon-based filler comprises a carbon nanotube material and a graphene nano sheet material, and the mass ratio of the carbon nanotube material to the graphene nano sheet material is (5-9): (1-5);
The second carbon-based filler comprises 6-10 parts of carbon nano tube material and 0-4 parts of graphene nano sheet material in parts by mass;
The carbon nano tube materials in the first carbon-based filler and the second carbon-based filler are independently unfunctionalized carbon nano tubes or functionalized carbon nano tubes, and the graphene nano sheet materials are independently unfunctionalized graphene nano sheets or functionalized graphene nano sheets; the functionalization modes in the functionalized carbon nanotubes and the functionalized graphene nanoplatelets are independently amino functionalization, carboxyl functionalization or hydroxyl functionalization.
2. The preparation method of claim 1, wherein the polyarylether composite fiber membrane is prepared by electrostatic spinning of a spinning solution comprising polyaryletherketimine and a first carbon-based filler; the content of the first carbon-based filler in the polyarylether composite fiber film is less than or equal to 30 weight percent.
3. The preparation method of claim 1, wherein the polyether-ether-ketone composite microsphere is prepared by sequentially pre-cooling a mixed dispersion liquid comprising polyether-ether-ketone, a second carbon-based filler and an aqueous polymer by liquid nitrogen and freeze-drying; the content of the second carbon-based filler in the polyether-ether-ketone composite microsphere is less than or equal to 30 weight percent.
4. The method of preparing the polyetheretherketone composite sheet according to claim 1, wherein the method of preparing the polyetheretherketone composite sheet comprises:
paving a part of polyether-ether-ketone composite microspheres in a single layer, and then performing first cold press molding to obtain a netlike sheet precursor;
and paving the residual polyether-ether-ketone composite microspheres at the non-connection point of the mesh sheet precursor for second cold press molding to obtain the polyether-ether-ketone composite sheet.
5. The preparation method of claim 4, wherein the mass ratio of the partial polyetheretherketone composite microsphere to the residual polyetheretherketone composite microsphere is 1: (0.3-1.5).
6. The method according to claim 4 or 5, wherein the pressure of the first cold press molding is 5 to 15MPa and the dwell time is 5 to 15min; the pressure of the second cold press molding is 5-35 MPa, and the pressure maintaining time is 5-20 min.
7. The method according to claim 1, wherein the hot press molding is performed at a temperature of 360 to 390 ℃, a pressure of 10 to 35MPa, and a holding time of 5 to 20 minutes.
8. The three-dimensional high-heat-conductivity electromagnetic shielding polyaryletherketone composite material prepared by the preparation method of any one of claims 1 to 7.
9. The use of the three-dimensional high thermal conductivity electromagnetic shielding polyaryletherketone composite material of claim 8 in aerospace, electronic and electrical, mechanical industry or military.
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