CN118957882A - A method for preparing high thermal conductivity poly(arylene ether nitrile) film - Google Patents
A method for preparing high thermal conductivity poly(arylene ether nitrile) film Download PDFInfo
- Publication number
- CN118957882A CN118957882A CN202411044155.5A CN202411044155A CN118957882A CN 118957882 A CN118957882 A CN 118957882A CN 202411044155 A CN202411044155 A CN 202411044155A CN 118957882 A CN118957882 A CN 118957882A
- Authority
- CN
- China
- Prior art keywords
- pen
- bpa
- bnns
- film
- fiber membrane
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 238000000034 method Methods 0.000 title claims abstract description 26
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 title claims description 37
- -1 poly(arylene ether nitrile Chemical class 0.000 title claims description 37
- 239000000835 fiber Substances 0.000 claims abstract description 79
- 238000009987 spinning Methods 0.000 claims abstract description 24
- 239000006185 dispersion Substances 0.000 claims abstract description 22
- 238000010041 electrostatic spinning Methods 0.000 claims abstract description 22
- 239000007921 spray Substances 0.000 claims abstract description 13
- 238000007731 hot pressing Methods 0.000 claims abstract description 9
- 239000012528 membrane Substances 0.000 claims description 52
- 239000000243 solution Substances 0.000 claims description 27
- 150000002825 nitriles Chemical class 0.000 claims description 20
- 229920000090 poly(aryl ether) Polymers 0.000 claims description 20
- 239000007788 liquid Substances 0.000 claims description 19
- 238000002347 injection Methods 0.000 claims description 17
- 239000007924 injection Substances 0.000 claims description 17
- 238000002360 preparation method Methods 0.000 claims description 17
- 229910052782 aluminium Inorganic materials 0.000 claims description 14
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 14
- 239000011888 foil Substances 0.000 claims description 14
- 230000008569 process Effects 0.000 claims description 13
- 238000003756 stirring Methods 0.000 claims description 11
- 238000007590 electrostatic spraying Methods 0.000 claims description 10
- 238000001816 cooling Methods 0.000 claims description 9
- 238000001132 ultrasonic dispersion Methods 0.000 claims description 8
- 238000001523 electrospinning Methods 0.000 claims description 2
- 238000000465 moulding Methods 0.000 claims 1
- 229910052582 BN Inorganic materials 0.000 abstract description 17
- 238000005507 spraying Methods 0.000 abstract description 16
- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 abstract description 13
- 239000011159 matrix material Substances 0.000 abstract description 12
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract description 7
- 239000011347 resin Substances 0.000 abstract description 7
- 229920005989 resin Polymers 0.000 abstract description 7
- 238000011049 filling Methods 0.000 abstract description 6
- 239000002135 nanosheet Substances 0.000 abstract description 6
- 238000010276 construction Methods 0.000 abstract description 3
- 229910002804 graphite Inorganic materials 0.000 abstract description 3
- 239000010439 graphite Substances 0.000 abstract description 3
- 230000001737 promoting effect Effects 0.000 abstract 1
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 75
- IISBACLAFKSPIT-UHFFFAOYSA-N Bisphenol A Natural products C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 25
- 230000000052 comparative effect Effects 0.000 description 20
- 239000002131 composite material Substances 0.000 description 11
- 229920000642 polymer Polymers 0.000 description 10
- 230000015556 catabolic process Effects 0.000 description 9
- 239000000463 material Substances 0.000 description 7
- 239000000945 filler Substances 0.000 description 5
- 229910021389 graphene Inorganic materials 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 238000011160 research Methods 0.000 description 4
- 230000017525 heat dissipation Effects 0.000 description 3
- 238000012546 transfer Methods 0.000 description 3
- 238000009825 accumulation Methods 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000002861 polymer material Substances 0.000 description 2
- 238000007592 spray painting technique Methods 0.000 description 2
- 230000009471 action Effects 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000002041 carbon nanotube Substances 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 230000000536 complexating effect Effects 0.000 description 1
- 239000011231 conductive filler Substances 0.000 description 1
- 239000013068 control sample Substances 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 229910052593 corundum Inorganic materials 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000004100 electronic packaging Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 229920001002 functional polymer Polymers 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- 230000020169 heat generation Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000004377 microelectronic Methods 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 239000002114 nanocomposite Substances 0.000 description 1
- 239000002121 nanofiber Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 229920000412 polyarylene Polymers 0.000 description 1
- 229920005594 polymer fiber Polymers 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000010345 tape casting Methods 0.000 description 1
- 229910001845 yogo sapphire Inorganic materials 0.000 description 1
Classifications
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
- D01F6/58—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolycondensation products
- D01F6/66—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolycondensation products from polyethers
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D1/00—Processes for applying liquids or other fluent materials
- B05D1/02—Processes for applying liquids or other fluent materials performed by spraying
- B05D1/04—Processes for applying liquids or other fluent materials performed by spraying involving the use of an electrostatic field
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D3/00—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials
- B05D3/02—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials by baking
- B05D3/0254—After-treatment
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D3/00—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials
- B05D3/12—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials by mechanical means
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
- B05D7/24—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials for applying particular liquids or other fluent materials
-
- D—TEXTILES; PAPER
- D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
- D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
- D04H1/00—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
- D04H1/70—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres characterised by the method of forming fleeces or layers, e.g. reorientation of fibres
- D04H1/72—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres characterised by the method of forming fleeces or layers, e.g. reorientation of fibres the fibres being randomly arranged
- D04H1/728—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres characterised by the method of forming fleeces or layers, e.g. reorientation of fibres the fibres being randomly arranged by electro-spinning
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Landscapes
- Engineering & Computer Science (AREA)
- Textile Engineering (AREA)
- Mechanical Engineering (AREA)
- Life Sciences & Earth Sciences (AREA)
- Wood Science & Technology (AREA)
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Manufacture Of Macromolecular Shaped Articles (AREA)
- Inorganic Fibers (AREA)
- Chemical Or Physical Treatment Of Fibers (AREA)
Abstract
本发明提供的一种高导热聚芳醚腈薄膜的制备方法，包括：1)配制BPA‑PEN纺丝液和BNNS分散液；2)通过静电纺丝对纤维进行取向，得到BPA‑PEN纤维膜；3)再将BNNS分散液静电喷涂在纤维膜表面，形成BPA‑PEN@BNNS叠喷纤维膜；4)对BPA‑PEN@BNNS叠喷纤维膜进行热压，得到高导热聚芳醚腈薄膜。本发明选取BPA‑PEN作为基体树脂进行静电纺丝实现纤维的取向，通过加入具有白石墨之称的剥离氮化硼纳米片填充基体，将BNNS静电喷涂在纤维表面后，再将重复叠喷得到的纤维膜进行热压得到高导热聚芳醚腈薄膜，进一步促进导热网络的构建，改善纤维膜的导热通路，得到导热系数高、综合性能优异的聚芳醚腈薄膜。
The present invention provides a method for preparing a high thermal conductivity polyarylethernitrile film, comprising: 1) preparing a BPA-PEN spinning solution and a BNNS dispersion; 2) orienting the fiber by electrostatic spinning to obtain a BPA-PEN fiber film; 3) electrostatically spraying the BNNS dispersion on the fiber film surface to form a BPA-PEN@BNNS spray-coated fiber film; 4) hot pressing the BPA-PEN@BNNS spray-coated fiber film to obtain a high thermal conductivity polyarylethernitrile film. The present invention selects BPA-PEN as a matrix resin for electrostatic spinning to achieve fiber orientation, adds a stripped boron nitride nanosheet filling matrix known as white graphite, electrostatically sprays BNNS on the fiber surface, and then hot presses the fiber film obtained by repeated spraying to obtain a high thermal conductivity polyarylethernitrile film, further promoting the construction of a thermal conductive network, improving the thermal conductive path of the fiber film, and obtaining a polyarylethernitrile film with high thermal conductivity and excellent comprehensive performance.
Description
Technical Field
The invention belongs to the technical field of material preparation, relates to the research of preparation of a nanocomposite and thermal performance thereof, and particularly relates to a preparation method of a high-heat-conductivity polyarylether nitrile film, in particular to a method for preparing a nanofiber membrane by an electrostatic spinning method and then performing hot pressing.
Background
Due to the trend toward miniaturization, automation and integration of microelectronic components and advanced mobile devices, the problem of heat dissipation is becoming a non-negligible issue. The problems of heat generation and accumulation in the operation process of electronic equipment and circuits may damage the system efficiency, so that the service life of electronic components is shortened by half, and meanwhile, a large amount of heat accumulation may cause problems of circuit aging, electric leakage and the like, so that the research of materials with high heat conductivity coefficients is urgently needed.
The polymer generally has the advantages of high temperature resistance, light weight, good processability, low cost and the like, and has been widely applied to the fields of electronic packaging and the like. Along with the diversification of the performance requirements of the 5G high-frequency communication on the used high-molecular materials, the single material is difficult to simultaneously meet the requirements of heat conduction performance, mechanical performance, dielectric property, processability and the like, so that the complexing is one of the important development trends of the future functional high-molecular materials. Specifically, the heat dissipation capacity of the polymer-based composite material depends on the thermal conductivity of the polymer-based composite material, and the higher the value, the more effective the heat dissipation capacity. However, the heat conduction constant of most polymers is only 0.1-0.5W/mK, which greatly limits the application of the polymer materials in heat transfer devices. The research shows that: the method for improving the heat conductivity of the polymer mainly comprises intrinsic type improvement and filling type improvement. Specifically, intrinsic heat conduction is mainly realized by changing the orientation of polymer molecular chains, crystallization, hydrogen bonds and other acting force angles to improve the heat conductivity; the filler type heat conduction is mainly studied by adding metal (Ag\Cu\Al, etc.), ceramic (BN\AlN\SiC\Si 3N4\Al2O3, etc.), carbon material (CNTs\GO\ GNSs \GNPs\CF), etc. and blending them into resin with specific requirements.
However, it is difficult to form a heat conductive path by filling a small amount of filler into the matrix resin, and electrospinning is a promising method for preparing a heat conductive composite material, which can arrange the oriented heat conductive filler in the fiber in a uniformly dispersed and highly oriented manner, thereby improving the heat conductive network and increasing the heat conductive capability of the material.
Poly (arylene ether nitrile) (Polyarylene ETHER NITRILE, PEN) is a functional polymer material with excellent mechanical properties, high temperature resistance and wear resistance and corrosion resistance, and is widely applied to the fields of military industry, aerospace and the like in recent years. However, the high polymer conducts heat through phonon diffusion, and factors such as entanglement of molecular chain segments, impurities, gaps and the like lead the heat conductivity of the high polymer to be very low, and the lower heat conductivity limits the application of the high polymer in the field of high-precision heat conduction.
In recent years, few reports on the study of the high-heat-conductivity polyarylether nitrile composite materials are provided. According to research, patent CN201610454177 discloses a poly (arylene ether nitrile)/nano aluminum oxide composite material and a preparation method thereof, wherein the mass ratio of filler to matrix resin is changed, a tape casting method is used for forming a film, the method is simple and feasible, but the formation condition of a heat conduction path is poor, so that the highest heat conduction coefficient in the system is lower than 0.5W/m.K, and in addition, the problems of poor compatibility and the like exist due to simple blending preparation, so that the mechanical property is destroyed; CN106046767a discloses a preparation technology of an in-situ thermal reduction polyaryl ether nitrile/graphene oxide high-thermal conductivity composite film, which utilizes excellent thermal conductivity of graphene oxide to improve thermal conductivity (34W/m.k) of the composite film and improves comprehensive performance through a thermal stretching technology, but the insulation of the film can be greatly damaged after the content of graphene is increased, so that the graphene cannot be applied as an interlayer dielectric in the electronic field.
Therefore, in combination with the above problems, the heat conductivity coefficient of the poly (arylene ether nitrile) is improved, and meanwhile, the high strength, the high modulus, the high decomposition temperature, the high glass transition temperature and the stable electrical performance of the poly (arylene ether nitrile) film can be maintained, so that the preparation method of the poly (arylene ether nitrile) film with excellent comprehensive performance is definitely provided, and the problem to be solved by the person skilled in the art is needed.
Disclosure of Invention
The invention aims to solve the problems in the prior art and provides a preparation method of a high-heat-conductivity polyarylether nitrile film. The invention prepares the high heat conduction poly (arylene ether nitrile) film by means of electrostatic spinning and hot press forming, prepares the peeled Boron Nitride Nano Sheet (BNNS) and bisphenol A poly (arylene ether nitrile) (BPA-PEN) into spinning solution, orients the fiber by electrostatic spinning, uniformly disperses BNNS on the fiber, and then carries out hot press on the fiber film to further promote the construction of a heat conduction network, thereby improving the heat conduction coefficient of the film, and the prepared film has excellent comprehensive performance and provides basic theory and operation basis for mass production of the high heat conduction insulating poly (arylene ether nitrile) film with excellent performance.
In order to achieve the above purpose, the technical scheme adopted by the invention is as follows:
a preparation method of a high-heat-conductivity polyarylether nitrile film comprises the following steps:
step 1, preparing a BPA-PEN@BNNS (bisphenol A type polyarylether nitrile@boron nitride) laminated fiber film;
1.1 adding BPA-PEN (bisphenol A type polyarylethernitrile) and DMF (N, N-dimethylformamide) into a beaker, and magnetically stirring for 1-2 h at 70-80 ℃ to obtain 0.05-0.15 g/mL of BPA-PEN spinning solution;
1.2 adding BNNS (boron nitride) into DMF (N, N-dimethylformamide), and performing ultrasonic dispersion for 8-12 hours at normal temperature to obtain BNNS dispersion liquid with the mass concentration of 0.1-0.3 g/mL;
1.3, placing the spinning solution obtained in the step 1.1 into an injector, setting the injection speed of a pump of the injector to be 1-3 mL/h, applying voltage to be 25-27 KV, enabling the working distance between the injector and a receiver to be 15-20 cm, enabling the rotating speed of the receiver to be 200-400 rpm/min, and carrying out electrostatic spinning for 1.5-2 h to obtain the BPA-PEN fiber membrane;
1.4, placing the BNNS dispersion liquid obtained in the step 1.2 into a syringe, setting the injection speed of a syringe pump to be 1-3 mL/h, applying voltage to be 25-27 KV, enabling the working distance between the syringe and a receiver to be 15-20 cm, enabling the rotating speed of the receiver to be 200-400 rpm/min, and continuing to carry out electrostatic spraying on the fiber membrane obtained in the step 1.3 for 1.5-2 h;
1.5 repeating the process of step 1.3-1.4 for 4-6 times to obtain the BPA-PEN@BNNS laminated fiber membrane;
step 2, preparing a poly (arylene ether nitrile) hot-pressed composite film;
Stripping the BPA-PEN@BNNS laminated fiber membrane obtained in the step 1.5 from an aluminum foil, and then placing the aluminum foil into a die to be hot-pressed for 10-20 min under the conditions of 10-20 MPa and 230-270 ℃ to obtain a BPA-PEN@BNNS laminated hot-pressed membrane; and naturally cooling the die to room temperature, and taking out the film to obtain the poly (arylene ether nitrile) film.
It should be noted that the above-listed process parameters were creatively obtained by the inventors through a large number of experiments. Wherein the BPA-PEN mass concentration, solution agitation time and temperature all have a direct effect on the uniformity and orientation of the fibrous film, and if deviated from the definition of the present application, the quality of the final product will not meet the intended purpose.
The invention provides a preparation method of a high-heat-conductivity polyarylether nitrile film, which has the following action mechanism:
Firstly, selecting BPA-PEN as matrix resin for electrostatic spinning to obtain a uniform and oriented fiber membrane, and then performing hot pressing to obtain a BPA-PEN film as a control sample; secondly, selecting a spray-overlaying mode, carrying out electrostatic spinning on the BPA-PEN to obtain a uniform and oriented fiber membrane, adding a peeling Boron Nitride Nano Sheet (BNNS) filling matrix with white graphite in an electrostatic spray-painting mode, and dispersing the BNNS along the axial direction of the polymer fiber in the spray-painting process, wherein the distance between the filling materials is reduced and mutually overlapped to form a heat conduction path, so that the heat conduction coefficient and the electric property are increased. In summary, BPA-PEN@BNNS is prepared into a fiber membrane by an electrostatic spinning method, and then hot pressing is carried out to obtain a film, and the contact distance between BNNS and BNNS is reduced by changing the contact mode of the fiber membrane and BNNS, so that the heat conduction path is improved, and the heat conduction performance is improved.
Compared with the prior art, the invention has the beneficial effects that:
1. According to the preparation method of the high-heat-conductivity polyaryl ether nitrile film, provided by the invention, BPA-PEN is selected as matrix resin to carry out electrostatic spinning to realize fiber orientation, a peeling Boron Nitride Nano Sheet (BNNS) filling matrix with white graphite is added, BNNS is subjected to electrostatic spraying on the surface of the fiber, and then the fiber film obtained by repeated overlapping spraying is subjected to hot pressing to obtain the high-heat-conductivity polyaryl ether nitrile film, so that the construction of a heat-conducting network is further promoted, the heat-conducting path of the fiber film is improved, and the polyaryl ether nitrile film with high heat conductivity and excellent comprehensive performance is obtained.
2. The invention provides a method for obtaining a high-heat-conductivity polyaryl ether nitrile film through electrostatic spinning and hot-press forming, which has the advantages of simple preparation process and low cost, and can realize large-scale production and application.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings that are required to be used in the embodiments or the description of the prior art will be briefly described below, and it is obvious that the drawings in the following description are only embodiments of the present invention, and that other drawings can be obtained according to the provided drawings without inventive effort for a person skilled in the art.
FIG. 1 is a profile of the cross-section of the BPA-PEN fibrous film (a) obtained in comparative example 1, the BPA-PEN@BNNS mixed spray fibrous film (b) obtained in comparative example 2, the fibrous film (c) obtained in comparative example 3, the BPA-PEN fibrous film (d) obtained in comparative example 1, the BPA-PEN@BNNS mixed spray fibrous film (e) obtained in comparative example 2, and the BPA-PEN@BNNS laminated spray fibrous film (f) obtained in example 1;
FIG. 2 is a graph of the out-of-plane thermal conductivity (a) and in-plane thermal conductivity (b) of the high thermal conductivity films prepared in examples 1-3 and the films prepared in comparative examples 1-4;
fig. 3 is a breakdown strength characterization of the high thermal conductivity films prepared in examples 1-3 and the films prepared in comparative examples 1-4.
Detailed Description
The following description of embodiments of the present invention will be made clearly and fully with reference to the accompanying drawings, in which it is evident that the embodiments described 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 embodiment of the invention discloses a preparation method of a high-heat-conductivity polyarylether nitrile film.
The present invention will be further specifically illustrated by the following examples, which are not to be construed as limiting the invention, but rather as falling within the scope of the present invention, for some non-essential modifications and adaptations of the invention that are apparent to those skilled in the art based on the foregoing disclosure.
The technical scheme of the invention will be further described below with reference to specific embodiments.
Example 1
A preparation method of a high-heat-conductivity polyarylether nitrile film comprises the following steps:
step 1, preparing a BPA-PEN@BNNS (bisphenol A type polyarylether nitrile@boron nitride) laminated fiber film;
1.1 adding BPA-PEN (bisphenol A type poly (arylene ether nitrile)) and DMF (N, N-dimethylformamide) into a beaker, magnetically stirring at 75 ℃ for 1h to obtain 0.1g/mL of BPA-PEN spinning solution;
1.2 adding BNNS (boron nitride) into DMF (N, N-dimethylformamide), and performing ultrasonic dispersion for 12 hours at normal temperature to obtain BNNS dispersion liquid with the mass concentration of 0.1 g/mL;
1.3, placing the spinning solution obtained in the step 1.1 into an injector, setting the injection speed of a pump of the injector to be 2mL/h, applying voltage to be 25KV, enabling the working distance between the injector and a receiver to be 18cm, enabling the rotating speed of the receiver to be 200rpm/min, and carrying out electrostatic spinning for 1.5h to obtain a BPA-PEN fiber membrane;
1.4, placing the BNNS dispersion liquid obtained in the step 1.2 into a syringe, setting the injection speed of a syringe pump to be 2mL/h, applying 25KV voltage, enabling the working distance between the syringe and a receiver to be 18cm, enabling the rotating speed of the receiver to be 200rpm/min, and continuing to carry out electrostatic spraying on the fiber membrane obtained in the step 1.3 for 1.5h;
1.5 repeating the process of step 1.3-1.4 for 4 times to obtain the BPA-PEN@BNNS laminated fiber membrane;
step 2, preparing a poly (arylene ether nitrile) hot-pressed composite film;
Stripping the BPA-PEN@BNNS laminated fiber membrane obtained in the step 1.5 from an aluminum foil, and then putting the aluminum foil into a die to be hot-pressed for 10min at the temperature of 20MPa and 260 ℃ to obtain a BPA-PEN@BNNS laminated hot-pressed membrane; and naturally cooling the die to room temperature, and taking out the film to obtain the poly (arylene ether nitrile) film.
The high thermal conductivity poly (arylene ether nitrile) film obtained in example 1 had an in-plane thermal conductivity of 3.26W/mK, an out-of-plane thermal conductivity of 0.38W/mK, and a breakdown strength of 92.32KV/mm.
Example 2
Step 1, preparing a BPA-PEN@BNNS (bisphenol A type polyarylether nitrile@boron nitride) laminated fiber film;
1.1 adding BPA-PEN (bisphenol A type poly (arylene ether nitrile)) and DMF (N, N-dimethylformamide) into a beaker, magnetically stirring at 75 ℃ for 1h to obtain 0.1g/mL of BPA-PEN spinning solution;
1.2 adding BNNS (boron nitride) into DMF (N, N-dimethylformamide), and performing ultrasonic dispersion for 12 hours at normal temperature to obtain BNNS dispersion liquid with the mass concentration of 0.2 g/mL;
1.3, placing the spinning solution obtained in the step 1.1 into an injector, setting the injection speed of a pump of the injector to be 2mL/h, applying voltage to be 25KV, enabling the working distance between the injector and a receiver to be 18cm, enabling the rotating speed of the receiver to be 200rpm/min, and carrying out electrostatic spinning for 1.5h to obtain a BPA-PEN fiber membrane;
1.4, placing the BNNS dispersion liquid obtained in the step 1.2 into a syringe, setting the injection speed of a syringe pump to be 2mL/h, applying 25KV voltage, enabling the working distance between the syringe and a receiver to be 18cm, enabling the rotating speed of the receiver to be 200rpm/min, and continuing to carry out electrostatic spraying on the fiber membrane obtained in the step 1.3 for 1.5h;
1.5 repeating the process of step 1.3-1.4 for 4 times to obtain the BPA-PEN@BNNS laminated fiber membrane;
step 2, preparing a poly (arylene ether nitrile) hot-pressed composite film;
Stripping the BPA-PEN@BNNS laminated fiber membrane obtained in the step 1.5 from an aluminum foil, and then putting the aluminum foil into a die to be hot-pressed for 10min at the temperature of 20MPa and 260 ℃ to obtain a BPA-PEN@BNNS laminated hot-pressed membrane; and naturally cooling the die to room temperature, and taking out the film to obtain the poly (arylene ether nitrile) film.
The high thermal conductivity poly (arylene ether nitrile) film obtained in example 2 had an in-plane thermal conductivity of 4.15W/mK, an out-of-plane thermal conductivity of 0.49W/mK, and a breakdown strength of 84.86KV/mm.
Example 3
Step 1, preparing a BPA-PEN@BNNS (bisphenol A type polyarylether nitrile@boron nitride) laminated fiber film;
1.1 adding BPA-PEN (bisphenol A type poly (arylene ether nitrile)) and DMF (N, N-dimethylformamide) into a beaker, magnetically stirring at 75 ℃ for 1h to obtain 0.1g/mL of BPA-PEN spinning solution;
1.2 adding BNNS (boron nitride) into DMF (N, N-dimethylformamide), and performing ultrasonic dispersion for 12 hours at normal temperature to obtain BNNS dispersion liquid with the mass concentration of 0.3 g/mL;
1.3, placing the spinning solution obtained in the step 1.1 into an injector, setting the injection speed of a pump of the injector to be 2mL/h, applying voltage to be 25KV, enabling the working distance between the injector and a receiver to be 18cm, enabling the rotating speed of the receiver to be 200rpm/min, and carrying out electrostatic spinning for 1.5h to obtain a BPA-PEN fiber membrane;
1.4, placing the BNNS dispersion liquid obtained in the step 1.2 into a syringe, setting the injection speed of a syringe pump to be 2mL/h, applying 25KV voltage, enabling the working distance between the syringe and a receiver to be 18cm, enabling the rotating speed of the receiver to be 200rpm/min, and continuing to carry out electrostatic spraying on the fiber membrane obtained in the step 1.3 for 1.5h;
1.5 repeating the process of step 1.3-1.4 for 2 times to obtain the BPA-PEN@BNNS laminated fiber membrane;
step 2, preparing a poly (arylene ether nitrile) hot-pressed composite film;
Stripping the BPA-PEN@BNNS laminated fiber membrane obtained in the step 1.5 from an aluminum foil, and then putting the aluminum foil into a die to be hot-pressed for 10min at the temperature of 20MPa and 260 ℃ to obtain a BPA-PEN@BNNS laminated hot-pressed membrane; and naturally cooling the die to room temperature, and taking out the film to obtain the poly (arylene ether nitrile) film.
The high thermal conductivity poly (arylene ether nitrile) film obtained in example 3 had an in-plane thermal conductivity of 5.98W/mK, an out-of-plane thermal conductivity of 0.62W/mK, and a breakdown strength of 69.52KV/mm.
In addition, in order to further illustrate the excellent effects of the technical scheme of the present invention, the present invention also provides the following comparative examples.
Comparative example 1
Step 1, adding BPA-PEN (bisphenol A type poly (arylene ether nitrile)) and DMF (N, N-dimethylformamide) into a beaker, and magnetically stirring for 1h at 75 ℃ to obtain a BPA-PEN spinning solution with the concentration of 0.1 g/mL;
Step 2, placing the spinning solution in an injector, setting the injection speed of the injector pump to be 2mL/h, applying the voltage to be 25KV, enabling the working distance between the injector and a receiver to be 18cm, enabling the rotating speed of the receiver to be 200rpm/min, and carrying out electrostatic spinning for 1.5h to obtain the BPA-PEN fiber membrane;
step 3, stripping the BPA-PEN fiber film from the aluminum foil, and then putting the film into a die to be hot-pressed for 10min under the conditions of 20MPa and 260 ℃ to obtain a BPA-PEN hot-pressed film; and naturally cooling the die to room temperature, and taking out the film to obtain the poly (arylene ether nitrile) film.
The in-plane thermal conductivity of the poly (arylene ether nitrile) film obtained in comparative example 1 was 0.54W/mK, the out-of-plane thermal conductivity was 0.067W/mK, and the breakdown strength was 90.45KV/mm.
Comparative example 2
Step 1, adding BPA-PEN (bisphenol A type poly (arylene ether nitrile)) and DMF (N, N-dimethylformamide) into a beaker, and magnetically stirring for 1h at 75 ℃ to obtain a 0.1g/mL BPA-PEN solution;
Step 2, adding BNNS (boron nitride) into DMF (N, N-dimethylformamide), and performing ultrasonic dispersion for 12 hours at normal temperature to obtain BNNS dispersion liquid with the mass concentration of 0.1 g/mL;
step 3, mixing the BPA-PEN solution and the BNNS dispersion liquid, and stirring for 1h at 75 ℃ to obtain a BPA-PEN@BNNS mixed spraying spinning solution;
Step 4, placing the BPA-PEN@BNNS mixed spinning solution obtained in the step 3 into an injector, setting the injection speed of a pump of the injector to be 2mL/h, setting the applied voltage to be 25KV, setting the working distance between the injector and a receiver to be 18cm, and carrying out electrostatic spinning for 2.5h at the rotating speed of the receiver of 200rpm/min to obtain the BPA-PEN@BNNS mixed spinning fiber membrane;
step 5, stripping the obtained BPA-PEN@BNNS mixed spraying fiber film from an aluminum foil, and then putting the stripped BPA-PEN@BNNS mixed spraying fiber film into a die to be hot-pressed for 10min at the temperature of 20MPa and 260 ℃ to obtain a BPA-PEN@BNNS mixed spraying hot-pressed film; and naturally cooling the die to room temperature, and taking out the film to obtain the BPA-PEN@BNNS mixed spraying fiber film.
The in-plane thermal conductivity of the mixed spray fibrous membrane obtained in comparative example 2 was 2.21W/mK, the out-of-plane thermal conductivity was 0.21W/mK, and the breakdown strength was 87.23KV/mm.
Comparative example 3
Step 1, adding BPA-PEN (bisphenol A type poly (arylene ether nitrile)) and DMF (N, N-dimethylformamide) into a beaker, and magnetically stirring for 1h at 75 ℃ to obtain a BPA-PEN spinning solution with the concentration of 0.1 g/mL;
Step 2, adding BNNS (boron nitride) into DMF (N, N-dimethylformamide), and performing ultrasonic dispersion for 12 hours at normal temperature to obtain BNNS dispersion liquid with the mass concentration of 0.1 g/mL;
Step 3, placing the spinning solution obtained in the step 1 into an injector, setting the injection speed of the injector pump to be 2mL/h, applying the voltage to be 25KV, enabling the working distance between the injector and a receiver to be 18cm, enabling the rotating speed of the receiver to be 200rpm/min, and carrying out electrostatic spinning for 1.5h to obtain the BPA-PEN fiber membrane;
Step 4, placing the BNNS dispersion liquid obtained in the step 2 into a syringe, setting the injection speed of a syringe pump to be 2mL/h, applying voltage to be 25KV, enabling the working distance between the syringe and a receiver to be 18cm, enabling the rotating speed of the receiver to be 200rpm/min, and continuing to carry out electrostatic spraying on the fiber membrane obtained in the step 3 for 1.5h;
Step 5, repeating the process of the steps 3-4 for 4 times to obtain the BPA-PEN@BNNS spray-laminated fiber membrane;
and 6, stripping the BPA-PEN@BNNS laminated fiber membrane obtained in the step 5 from the aluminum foil to obtain the laminated fiber membrane.
The in-plane thermal conductivity of the laminated fiber film obtained in comparative example 3 was 0.47W/mK, the out-of-plane thermal conductivity was 0.053W/mK, and the breakdown strength was 10.77KV/mm.
Comparative example 4
Step 1, adding BPA-PEN (bisphenol A type poly (arylene ether nitrile)) and DMF (N, N-dimethylformamide) into a beaker, and magnetically stirring for 1h at 75 ℃ to obtain a 0.1g/mL BPA-PEN solution;
Step 2, adding BNNS (boron nitride) into DMF (N, N-dimethylformamide), and performing ultrasonic dispersion for 12 hours at normal temperature to obtain BNNS dispersion liquid with the mass concentration of 0.1 g/mL;
step 3, mixing the BPA-PEN solution and the BNNS dispersion liquid, and stirring for 1h at 75 ℃ to obtain a BPA-PEN@BNNS mixed spraying spinning solution;
Step 4, placing the BPA-PEN@BNNS mixed spinning solution obtained in the step 3 into an injector, setting the injection speed of a pump of the injector to be 2mL/h, setting the applied voltage to be 27KV, setting the working distance between the injector and a receiver to be 18cm, and carrying out electrostatic spinning for 2.5h at the rotating speed of the receiver of 200rpm/min to obtain the BPA-PEN@BNNS mixed spinning fiber membrane;
step 5, stripping the obtained BPA-PEN@BNNS mixed spraying fiber film from an aluminum foil, and then putting the stripped BPA-PEN@BNNS mixed spraying fiber film into a die to be hot-pressed for 10min at the temperature of 20MPa and 260 ℃ to obtain a BPA-PEN@BNNS mixed spraying hot-pressed film; and naturally cooling the die to room temperature, and taking out the film to obtain the BPA-PEN@BNNS mixed spraying fiber film.
The in-plane thermal conductivity of the mixed spray fibrous membrane obtained in comparative example 4 was 2.69W/mK, the out-of-plane thermal conductivity was 0.25W/mK, and the breakdown strength was 88.84KV/mm.
Thermal conductivity: the peeled boron nitride nano-sheet has large specific surface area, and the unique lamellar structure can effectively reduce the interface thermal resistance between the boron nitride nano-sheet and the matrix resin and improve the heat conduction efficiency; thus, the overall thermal conductivity of examples 1-3 is improved as compared to comparative example 1; examples 1-3 differ in electrostatic spray process from comparative example 2 in that the spray process of examples resulted in BNNS being oriented along PEN with increased degrees of orientation and enhanced heat transfer.
As can be seen from FIG. 1, (a) BPA-PEN fiber film, which has uniform fiber thickness and high degree of orientation; (b) BPA-PEN@BNNS mixed spraying fiber membrane has defects on the surface of the fiber, the fiber diameter is uneven, and the BNNS agglomeration phenomenon is obvious; (c) The BPA-PEN@BNNS laminated fiber membrane has the advantages that the BNNS is good in dispersion condition on the fiber surface, the particle size of the BNNS is smaller than that of BNNS sprayed by the mixed solution, and the distance between the BPA-PEN and the BNNS is smaller; the patterns (d) - (f) are respectively the profiles of the cross sections of the hot-pressed films sprayed by BPA-PEN, BPA-PEN@BNNS mixed spraying and BPA-PEN@BNNS laminated spraying, and the (f) can be used for observing that a good heat conduction network is formed between the BPE-PEN and the BNNS. These phenomena indicate that the interfacial thermal resistance between the matrix and the filler is reduced, forming an effective, complex thermally conductive network, thus raising λ. In summary, in example 1, compared with comparative example 3, the variables are whether to perform the hot pressing treatment, and after the hot pressing treatment, the air between the fibers is reduced, the heat conduction network is improved, and the heat transfer efficiency is effectively improved, so that the heat conductivity coefficient is improved after the heat treatment.
Compared with comparative example 1, the other examples all added with high thermal conductivity filler BNNS, a continuous thermal conductivity network is formed in the matrix, and thus the thermal conductivity coefficient is improved.
As shown in fig. 3, the breakdown strength of examples 1-3 decreases with increasing loading of BNNS due to increasing interfacial resistance of the matrix polymer and BNNS and decreasing electrical properties.
The previous description of the disclosed embodiments is provided to enable any person skilled in the art to make or use the present invention. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments without departing from the spirit or scope of the invention. Thus, the present invention is not intended to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.
Claims (5)
1. The preparation method of the high-heat-conductivity polyaryl ether nitrile film is characterized in that the high-heat-conductivity polyaryl ether nitrile film is obtained by means of electrostatic spinning and hot press molding, and comprises the following steps:
Step 1, preparing BPA-PEN spinning solution and BNNS dispersion liquid;
Step 2, orienting the fiber through electrostatic spinning to obtain a BPA-PEN fiber membrane;
step 3, electrostatic spraying BNNS dispersion liquid on the surface of the fiber membrane to form a BPA-PEN@BNNS laminated fiber membrane;
And step 4, hot-pressing the BPA-PEN@BNNS laminated fiber membrane to obtain the high-heat-conductivity polyarylether nitrile film.
2. The method for preparing the high thermal conductivity poly (arylene ether nitrile) film according to claim 1, wherein the step 2 of electrospinning comprises the following steps: placing the BPA-PEN spinning solution in an injector, setting the injection speed of the injector pump to be 1-3 mL/h, applying the voltage to be 25-27 KV, enabling the working distance between the injector and a receiver to be 15-20 cm, enabling the rotating speed of the receiver to be 200-400 rpm/min, and carrying out electrostatic spinning for 1.5-2 h to obtain the BPA-PEN fiber membrane.
3. The method for preparing the high thermal conductivity poly (arylene ether nitrile) film according to claim 1, wherein the electrostatic spraying process in the step 3 is as follows: the BNNS dispersion liquid is placed in an injector, the injection speed of the injector pump is set to be 1-3 mL/h, the applied voltage is 25-27 KV, the working distance between the injector and a receiver is 15-20 cm, the rotating speed of the receiver is 200-400 rpm/min, and electrostatic spraying is carried out on the obtained BPA-PEN fiber membrane for 1.5-2 h.
4. The method for preparing the high thermal conductivity poly (arylene ether nitrile) film according to claim 1, wherein the hot pressing process in the step 4 is as follows: stripping the obtained BPA-PEN@BNNS laminated spray fiber membrane, and then placing the stripped BPA-PEN@BNNS laminated spray fiber membrane into a die to be hot-pressed for 10-20 min under the conditions of 10-20 MPa and 230-270 ℃ to obtain a BPA-PEN@BNNS laminated spray hot-pressed membrane; and naturally cooling the die to room temperature, and taking out the film to obtain the poly (arylene ether nitrile) film.
5. The preparation method of the high-heat-conductivity polyarylether nitrile film is characterized by comprising the following steps of:
step 1, preparing a BPA-PEN@BNNS laminated fiber membrane;
1.1 adding BPA-PEN into DMF, magnetically stirring for 1-2 h at 70-80 ℃ to obtain 0.05-0.15 g/mL BPA-PEN spinning solution;
1.2 adding BNNS into DMF, and performing ultrasonic dispersion for 8-12 hours at normal temperature to obtain BNNS dispersion liquid with the mass concentration of 0.1-0.3 g/mL;
1.3, placing the spinning solution obtained in the step 1.1 into an injector, setting the injection speed of a pump of the injector to be 1-3 mL/h, applying voltage to be 25-27 KV, enabling the working distance between the injector and a receiver to be 15-20 cm, enabling the rotating speed of the receiver to be 200-400 rpm/min, and carrying out electrostatic spinning for 1.5-2 h to obtain the BPA-PEN fiber membrane;
1.4, placing the BNNS dispersion liquid obtained in the step 1.2 into a syringe, setting the injection speed of a syringe pump to be 1-3 mL/h, applying voltage to be 25-27 KV, enabling the working distance between the syringe and a receiver to be 15-20 cm, enabling the rotating speed of the receiver to be 200-400 rpm/min, and continuing to carry out electrostatic spraying on the fiber membrane obtained in the step 1.3 for 1.5-2 h;
1.5 repeating the process of step 1.3-1.4 for 4-6 times to obtain the BPA-PEN@BNNS laminated fiber membrane;
step 2, preparing a poly (arylene ether nitrile) film;
Stripping the BPA-PEN@BNNS laminated fiber membrane obtained in the step 1 from an aluminum foil, and then placing the aluminum foil into a die to be hot-pressed for 10-20 min under the conditions of 10-20 MPa and 230-270 ℃ to obtain a BPA-PEN@BNNS laminated hot-pressed membrane; and naturally cooling the die to room temperature, and taking out the film to obtain the poly (arylene ether nitrile) film.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202411044155.5A CN118957882A (en) | 2024-07-31 | 2024-07-31 | A method for preparing high thermal conductivity poly(arylene ether nitrile) film |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202411044155.5A CN118957882A (en) | 2024-07-31 | 2024-07-31 | A method for preparing high thermal conductivity poly(arylene ether nitrile) film |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN118957882A true CN118957882A (en) | 2024-11-15 |
Family
ID=93397634
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202411044155.5A Pending CN118957882A (en) | 2024-07-31 | 2024-07-31 | A method for preparing high thermal conductivity poly(arylene ether nitrile) film |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN118957882A (en) |
-
2024
- 2024-07-31 CN CN202411044155.5A patent/CN118957882A/en active Pending
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN108250747B (en) | Thermoplastic polyetherimide insulating and heat-conducting composite material and preparation method thereof | |
| CN108943779A (en) | A kind of preparation method of high filler loading PTFE composite membrane material | |
| CN103525005B (en) | The preparation method of the high heat conduction ternary of low sizing content nano-micro structure epoxy composite material | |
| CN111424421B (en) | Carbon fiber composite felt and method for enhancing heat conduction and electric conduction performance of polymer composite material | |
| CN106832877A (en) | A kind of preparation method of vertical orientated boron nitride/high polymer insulating heat-conduction material | |
| CN111500070A (en) | Carbon fiber oriented thermal interface material and preparation method thereof | |
| CN111171449B (en) | High-thermal-conductivity polypropylene/graphene composite material and preparation method thereof | |
| CN102477226B (en) | A kind of high current resistant thermistor polymer composite material and preparation method thereof | |
| CN111534016B (en) | Electronic packaging material with heat conduction and electromagnetic shielding performance and preparation method thereof | |
| JP2008049607A (en) | Heat-conductive laminate with bonded thin film of electrical insulation | |
| CN106480533A (en) | A kind of polymide dielectric heat-conductive composite material and preparation method thereof | |
| CN103497411A (en) | Flexible high-thermal-conductivity insulating polymer composite and preparation method thereof | |
| CN113337103A (en) | Low-dielectric and high-thermal-conductivity polymer-based composite material and preparation method thereof | |
| CN103319893A (en) | Preparation method of high-heat-conducting polyphenylene sulfide material and prepared material | |
| CN110105761A (en) | Graphene/polyphenylene sulfide electromagnetic shielding composite material and preparation method thereof | |
| CN118957882A (en) | A method for preparing high thermal conductivity poly(arylene ether nitrile) film | |
| CN114031934A (en) | Polyamide composite material with high thermal conductivity coefficient and preparation method thereof | |
| CN111187514A (en) | Insulating and heat-conducting PPS composite material and preparation method thereof | |
| CN104130476B (en) | A kind of preparation method of wide temperature range height heat conductive rubber based composites | |
| CN116083060A (en) | Composite heat and electricity conducting material formed by carbon fiber based on ASPN (advanced manufacturing process) treatment technology | |
| CN107139371A (en) | Microwave forming method for Thermocurable polyimide sheet material | |
| CN100439886C (en) | An electric heating composite material for temperature measurement and its preparation method | |
| CN115284713B (en) | Polymer composite heat-conducting heterogeneous fiber membrane and preparation method thereof | |
| CN102412027B (en) | Manufacturing method of H-level and 200-level electromagnetic wire | |
| CN106380853B (en) | Preparation method of spherical aluminum nitride-silicon rubber composite material |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination |