CN116288944B - Preparation method and application of high-heat-conductivity multi-layer gradient structure epoxy resin composite medium - Google Patents
Preparation method and application of high-heat-conductivity multi-layer gradient structure epoxy resin composite medium Download PDFInfo
- Publication number
- CN116288944B CN116288944B CN202310285867.5A CN202310285867A CN116288944B CN 116288944 B CN116288944 B CN 116288944B CN 202310285867 A CN202310285867 A CN 202310285867A CN 116288944 B CN116288944 B CN 116288944B
- Authority
- CN
- China
- Prior art keywords
- epoxy resin
- composite medium
- heat
- resin composite
- mixed solution
- 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.)
- Active
Links
- 239000003822 epoxy resin Substances 0.000 title claims abstract description 155
- 229920000647 polyepoxide Polymers 0.000 title claims abstract description 155
- 239000002131 composite material Substances 0.000 title claims abstract description 124
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- 239000004417 polycarbonate Substances 0.000 claims abstract description 42
- 229920000515 polycarbonate Polymers 0.000 claims abstract description 42
- 239000000945 filler Substances 0.000 claims abstract description 35
- 238000009987 spinning Methods 0.000 claims abstract description 27
- 238000000034 method Methods 0.000 claims abstract description 13
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 66
- 239000011259 mixed solution Substances 0.000 claims description 41
- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 claims description 26
- 238000003756 stirring Methods 0.000 claims description 26
- 229910052582 BN Inorganic materials 0.000 claims description 25
- 239000000243 solution Substances 0.000 claims description 24
- 239000002243 precursor Substances 0.000 claims description 23
- 239000003795 chemical substances by application Substances 0.000 claims description 17
- 239000002245 particle Substances 0.000 claims description 16
- AHDSRXYHVZECER-UHFFFAOYSA-N 2,4,6-tris[(dimethylamino)methyl]phenol Chemical compound CN(C)CC1=CC(CN(C)C)=C(O)C(CN(C)C)=C1 AHDSRXYHVZECER-UHFFFAOYSA-N 0.000 claims description 14
- 238000003760 magnetic stirring Methods 0.000 claims description 12
- 239000007788 liquid Substances 0.000 claims description 11
- 238000010041 electrostatic spinning Methods 0.000 claims description 9
- 238000001035 drying Methods 0.000 claims description 7
- VYKXQOYUCMREIS-UHFFFAOYSA-N methylhexahydrophthalic anhydride Chemical compound C1CCCC2C(=O)OC(=O)C21C VYKXQOYUCMREIS-UHFFFAOYSA-N 0.000 claims description 7
- 238000004506 ultrasonic cleaning Methods 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 5
- MWSKJDNQKGCKPA-UHFFFAOYSA-N 6-methyl-3a,4,5,7a-tetrahydro-2-benzofuran-1,3-dione Chemical compound C1CC(C)=CC2C(=O)OC(=O)C12 MWSKJDNQKGCKPA-UHFFFAOYSA-N 0.000 claims description 2
- 239000010410 layer Substances 0.000 abstract description 28
- 229920000642 polymer Polymers 0.000 abstract description 16
- 239000002356 single layer Substances 0.000 abstract description 15
- 239000011256 inorganic filler Substances 0.000 abstract description 14
- 229910003475 inorganic filler Inorganic materials 0.000 abstract description 14
- 238000010292 electrical insulation Methods 0.000 abstract description 6
- 238000009413 insulation Methods 0.000 abstract description 5
- 239000004593 Epoxy Substances 0.000 abstract description 3
- 239000000835 fiber Substances 0.000 abstract description 2
- 239000011810 insulating material Substances 0.000 abstract description 2
- 230000006798 recombination Effects 0.000 abstract description 2
- 238000005215 recombination Methods 0.000 abstract description 2
- 230000002195 synergetic effect Effects 0.000 abstract description 2
- 230000000052 comparative effect Effects 0.000 description 31
- 238000001228 spectrum Methods 0.000 description 14
- 230000015556 catabolic process Effects 0.000 description 13
- 238000009826 distribution Methods 0.000 description 12
- 239000000463 material Substances 0.000 description 11
- 230000001965 increasing effect Effects 0.000 description 9
- 238000012360 testing method Methods 0.000 description 8
- 238000011161 development Methods 0.000 description 7
- 239000011159 matrix material Substances 0.000 description 7
- 238000011160 research Methods 0.000 description 5
- 230000033228 biological regulation Effects 0.000 description 4
- 230000005540 biological transmission Effects 0.000 description 4
- 238000012512 characterization method Methods 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 239000000969 carrier Substances 0.000 description 3
- 230000007423 decrease Effects 0.000 description 3
- 230000007547 defect Effects 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 238000002347 injection Methods 0.000 description 3
- 239000007924 injection Substances 0.000 description 3
- 239000004973 liquid crystal related substance Substances 0.000 description 3
- 238000002844 melting Methods 0.000 description 3
- 230000008018 melting Effects 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000000149 penetrating effect Effects 0.000 description 3
- 239000004033 plastic Substances 0.000 description 3
- 230000008901 benefit Effects 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 239000011231 conductive filler Substances 0.000 description 2
- 230000003247 decreasing effect Effects 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000005684 electric field Effects 0.000 description 2
- 238000004100 electronic packaging Methods 0.000 description 2
- 238000011049 filling Methods 0.000 description 2
- 230000001788 irregular Effects 0.000 description 2
- 238000002372 labelling Methods 0.000 description 2
- 238000004377 microelectronic Methods 0.000 description 2
- 238000005457 optimization Methods 0.000 description 2
- 230000010287 polarization Effects 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- 238000007711 solidification Methods 0.000 description 2
- 230000008023 solidification Effects 0.000 description 2
- 238000005303 weighing 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 1
- 150000008064 anhydrides Chemical class 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000002041 carbon nanotube Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000003989 dielectric material Substances 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 239000012776 electronic material Substances 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 239000005022 packaging material Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 239000011232 storage material Substances 0.000 description 1
- 238000009210 therapy by ultrasound Methods 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- 239000004416 thermosoftening plastic Substances 0.000 description 1
- 238000003466 welding Methods 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
- D01F8/00—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof
- D01F8/04—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from synthetic polymers
- D01F8/16—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from synthetic polymers with at least one other macromolecular compound obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds as constituent
-
- 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
- D01F1/00—General methods for the manufacture of artificial filaments or the like
- D01F1/02—Addition of substances to the spinning solution or to the melt
- D01F1/10—Other agents for modifying properties
-
- 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
- D04H1/40—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties
- D04H1/42—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties characterised by the use of certain kinds of fibres insofar as this use has no preponderant influence on the consolidation of the fleece
- D04H1/4382—Stretched reticular film fibres; Composite fibres; Mixed fibres; Ultrafine fibres; Fibres for artificial leather
- D04H1/43825—Composite fibres
-
- 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
Landscapes
- Engineering & Computer Science (AREA)
- Textile Engineering (AREA)
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Manufacturing & Machinery (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
A preparation method and application of a high-heat-conductivity multi-layer gradient structure epoxy resin composite medium relate to the technical field of heat-conducting insulating materials. The invention aims to solve the problem that the heat conduction performance of the epoxy resin is improved and the insulating performance of the composite material is reduced by adopting the epoxy resin doped with inorganic filler at present. The method comprises the following steps: the invention utilizes the synergistic effect between the polycarbonate molecular chain and the epoxy polymer molecular chain to help the stability and recombination of the spinning fiber, and the inorganic filler is distributed in a gradient way along the out-of-plane direction, thus realizing a multi-layer composite medium in which the filler is distributed in a gradient structure in the polymer composite material. The unique structure enables the multilayer gradient film to have excellent out-of-plane heat conductivity and excellent electrical insulation performance, and compared with a single-layer epoxy resin composite film, the thermal conductivity and the insulation performance are greatly improved. The invention can obtain a preparation method and application of the epoxy resin composite medium with the high heat conduction multilayer gradient structure.
Description
Technical Field
The invention relates to the technical field of heat-conducting insulating materials, in particular to a preparation method and application of a high-heat-conducting multilayer gradient structure epoxy resin composite medium.
Background
The electronic material is the foundation of the development of the microelectronic industry, the epoxy plastic package material which is the main structural material for producing integrated circuits is also rapidly developed along with the development of chip technology, and the development of the plastic package material technology greatly promotes the development of the microelectronic industry. At present, integrated circuits are advanced to the development of high integration, wiring miniaturization and surface mounting technology, and the research and development trend of plastic packaging materials suitable for the advanced development is to enable the materials to have the performance characteristics of high reliability, high heat conduction, high welding resistance, high glass transition temperature, low expansion, low dielectric constant, easy processing and the like.
According to the current state of research, two methods are mainly adopted at present to improve the heat conduction performance of epoxy resin: firstly, the intrinsic modification research for regulating and controlling the heat conducting performance of the epoxy resin based on a molecular structure is carried out, namely, a series of regulation and control are carried out on the molecular chain structure of the epoxy resin, a regular and ordered liquid crystal structure is formed in the epoxy resin matrix to improve the crystallinity or orientation degree of the epoxy resin, a material is endowed with some new physical properties and mechanical properties, and the heat conductivity of the epoxy resin material can be improved, however, the regulation and control of the molecular structure based on the molecular structure is higher in most melting points of epoxy resin monomers, the curing process is completed under high-temperature melting, the curing process difficulty is higher, and the cost is higher. Secondly, based on the modified research of the heat conducting property of the epoxy resin doped with the inorganic high-heat-conductivity filler, namely, the filled heat conducting epoxy resin is obtained by adding some high-heat-conductivity inorganic micron and nano fillers into the epoxy resin material and combining the preparation process optimization.
However, the doping of the inorganic filler affects the insulation of the composite material while improving the heat conduction performance of the epoxy resin, so the problem and the challenge of developing the filled epoxy resin with both high heat conduction and high insulation still exist. In recent years, due to complementarity of different layers, construction of a multilayer structure has proved to be an effective method for manufacturing high-performance functional composite materials and energy storage materials, and meanwhile, the distribution of heat conducting fillers in a polymer composite material is found to play an important role in heat conductivity and electric insulation performance, but a multilayer gradient structure has not been explored at present for the design of heat conducting performance improvement.
Disclosure of Invention
The invention aims to solve the problem that the heat conduction performance of the epoxy resin is improved and the insulating performance of a composite material is reduced by adopting the epoxy resin doped with inorganic filler at present, and provides a preparation method and application of a high-heat-conduction multi-layer gradient structure epoxy resin composite medium.
The preparation method of the epoxy resin composite medium with the high heat conduction multilayer gradient structure comprises the following steps:
step one: 10 parts of N, N-dimethylformamide solution with the same volume is correspondingly added into a No. 1-10 container, 10 parts of hexagonal boron nitride is additionally taken, and the mass ratio of the added hexagonal boron nitride is 0:2:4:6:8:8:6:4:2:0 or 3:3.5:4:4.5:5:5:4.5:4:3.5:3 are added into a No. 1-10 container in sequence, and after magnetic stirring for 30-50 min, ultrasonic cleaning is carried out for 40-60 min to obtain 10 groups of fillers;
step two: adding 10 equal parts of epoxy resin and N, N-dimethylformamide into 10 groups of fillers in the first step, adding equal amounts of a curing agent and 2,4, 6-tris (dimethylaminomethyl) phenol into a No. 1-10 container while magnetically stirring, and uniformly mixing to obtain 10 groups of epoxy resin mixed solutions, wherein the ratio of the mass of the epoxy resin, the volume of the curing agent and the volume of the 2,4, 6-tris (dimethylaminomethyl) phenol is (100-120): (80-100): 1, a step of;
step three: adding equal amount of polycarbonate particles into the 10 groups of epoxy resin mixed solution in the second step, and magnetically stirring until the polycarbonate particles are completely dissolved to obtain 10 groups of epoxy resin/polycarbonate mixed solution spinning precursor liquid;
the total mass of hexagonal boron nitride, mass ratio of each part of epoxy resin to each part of polycarbonate particles is 1:0.2:0.2;
step four: and (3) correspondingly extracting 10 groups of epoxy resin/polycarbonate mixed solution spinning precursor solutions in the third step by using 10 injectors, sequentially carrying out electrostatic spinning on the 10 groups of epoxy resin/polycarbonate mixed solution spinning precursor solutions according to the sequence of No. 1-10 containers to obtain 10 layers of integrated composite medium films, carrying out gradient temperature curing on the 10 layers of integrated composite medium films, and drying to obtain the epoxy resin composite medium with the high-heat-conductivity multilayer gradient structure.
The application of the high-heat-conductivity multi-layer gradient structure epoxy resin composite medium in electronic packaging and/or electrical equipment.
The principle of the invention is as follows:
according to the invention, thermosetting epoxy resin and thermoplastic polycarbonate are mixed as a matrix, hexagonal boron nitride (h-BN) is used as inorganic doping, and the synergistic effect between polycarbonate molecular chains and epoxy polymer molecular chains is utilized to help the stability and recombination of spinning fibers, and inorganic fillers are distributed in a gradient manner along the out-of-plane direction, so that a multilayer composite medium in which the fillers are distributed in a gradient structure in a polymer composite material is realized. The unique structure enables the multilayer gradient film to have excellent out-of-plane heat conductivity and excellent electrical insulation performance, and compared with a single-layer epoxy resin composite film, the thermal conductivity and the insulation performance are greatly improved.
The invention has the beneficial effects that:
1. at present, the prior art has the following two preparation methods of epoxy resin composite materials:
(1) The traditional liquid crystal epoxy resin is based on intrinsic modification research of molecular structure regulation and control of the heat conducting performance of the epoxy resin, namely, a series of regulation and control are carried out on the molecular chain structure of the epoxy resin, a regular and ordered liquid crystal structure is formed inside an epoxy resin matrix to improve the crystallinity or orientation degree of the epoxy resin, and further the heat conductivity of an epoxy resin material is improved. The epoxy resin molecules are regulated to cause the melting point to be higher, so that the curing temperature is high and the curing difficulty is high for curing in a molten state.
(2) Based on the research of modification of the heat conducting property of the epoxy resin doped with the inorganic high-heat conducting filler, namely by adding some high-heat conducting inorganic micron and nano fillers such as alumina (Al) 2 O 3 ) Boron Nitride (BN), carbon Nanotubes (CNTs) and the like, and the preparation process is combined to optimize to obtain the filled heat-conducting epoxy resin. The addition of such highly thermally conductive fillers would, without exception, destroy the electrical insulation properties of the composite.
Compared with the traditional two epoxy resin composite material preparation methods, the method has the advantages of lower solidification difficulty and lower solidification cost, and can greatly improve the electrical insulation property of the polymer.
2. The epoxy resin composite medium with the high heat conduction multilayer gradient structure prepared by the invention reveals the optimization characteristic of the electrical insulation performance of the epoxy resin composite dielectric medium with the layered structure. The inorganic filler is distributed in a gradient structure in the matrix, can greatly obstruct the injection and transportation of charged carriers, plays a role in isolating an electron transmission path, and forms a weak electric field area around two different interfaces, which is considered to be a main reason for obtaining higher breakdown strength by obstructing the development of an electric tree, and the composition can increase the propagation time of a breakdown channel at the interface position by prolonging the breakdown path, thereby enhancing the breakdown strength. In addition, the interface also shows a barrier effect due to the change of breakdown starting conditions, so that the electrical insulation property of the composite medium can be well improved while the thermal conductivity of the polymer composite material is improved.
The invention can obtain a preparation method and application of the epoxy resin composite medium with the high heat conduction multilayer gradient structure.
Drawings
FIG. 1 is a cross-sectional scanning electron microscope test chart of an epoxy resin composite film in comparative example 1;
FIG. 2 is a cross-sectional scanning electron microscope test chart of a single-layer uniform epoxy resin composite medium in comparative example 2;
FIG. 3 is a line scan energy spectrum of the B element at the scribe line in FIG. 2;
FIG. 4 is a line scan energy spectrum of the N element at the scribe line in FIG. 2;
FIG. 5 is a cross-sectional scanning electron microscope test chart of the epoxy resin composite medium with the high thermal conductivity multilayer gradient structure in example 1;
FIG. 6 is a line scan energy spectrum of the B element at the scribe line in FIG. 5;
FIG. 7 is a line scan energy spectrum of the N element at the scribe line in FIG. 5;
FIG. 8 is a cross-sectional scanning electron microscope test chart of the epoxy resin composite medium with the high thermal conductivity multilayer gradient structure in example 2;
FIG. 9 is a line scan energy spectrum of the B element at the scribe line in FIG. 8;
FIG. 10 is a line scan energy spectrum of the N element at the scribe line in FIG. 8;
FIG. 11 is a graph showing breakdown characteristics of each of the epoxy resin composite media of examples 1-2 and comparative examples 1-2, ■ showing the epoxy resin composite film of comparative example 1, +.;
FIG. 12 is a graph of dielectric properties of each of the epoxy resin composite media of examples 1-2 and comparative examples 1-2, ■ showing the epoxy resin composite film of comparative example 1, +.;
FIG. 13 is a dielectric loss image of each of the epoxy resin composite media of examples 1-2 and comparative examples 1-2, ■ showing the epoxy resin composite film of comparative example 1, +.;
annotation: the scribe line in fig. 2, 5 and 7 is the element line scanning position.
Detailed Description
The first embodiment is as follows: the preparation method of the epoxy resin composite medium with the high-heat-conductivity multilayer gradient structure in the embodiment comprises the following steps:
step one: 10 parts of N, N-dimethylformamide solution with the same volume is correspondingly added into a No. 1-10 container, 10 parts of hexagonal boron nitride is additionally taken, and the mass ratio of the added hexagonal boron nitride is 0:2:4:6:8:8:6:4:2:0 or 3:3.5:4:4.5:5:5:4.5:4:3.5:3 are added into a No. 1-10 container in sequence, and after magnetic stirring for 30-50 min, ultrasonic cleaning is carried out for 40-60 min to obtain 10 groups of fillers;
step two: adding 10 equal parts of epoxy resin and N, N-dimethylformamide into 10 groups of fillers in the first step, adding equal amounts of a curing agent and 2,4, 6-tris (dimethylaminomethyl) phenol into a No. 1-10 container while magnetically stirring, and uniformly mixing to obtain 10 groups of epoxy resin mixed solutions, wherein the ratio of the mass of the epoxy resin, the volume of the curing agent and the volume of the 2,4, 6-tris (dimethylaminomethyl) phenol is (100-120): (80-100): 1, a step of;
step three: adding equal amount of polycarbonate particles into the 10 groups of epoxy resin mixed solution in the second step, and magnetically stirring until the polycarbonate particles are completely dissolved to obtain 10 groups of epoxy resin/polycarbonate mixed solution spinning precursor liquid;
the total mass of hexagonal boron nitride, mass ratio of each part of epoxy resin to each part of polycarbonate particles is 1:0.2:0.2;
step four: and (3) correspondingly extracting 10 groups of epoxy resin/polycarbonate mixed solution spinning precursor solutions in the third step by using 10 injectors, sequentially carrying out electrostatic spinning on the 10 groups of epoxy resin/polycarbonate mixed solution spinning precursor solutions according to the sequence of No. 1-10 containers to obtain 10 layers of integrated composite medium films, carrying out gradient temperature curing on the 10 layers of integrated composite medium films, and drying to obtain the epoxy resin composite medium with the high-heat-conductivity multilayer gradient structure.
The second embodiment is as follows: the present embodiment differs from the specific embodiment in that: the ratio of the total mass of hexagonal boron nitride to the volume of the N, N-dimethylformamide solution in each set of containers in step one was 1g: (0.8-1) mL.
The other steps are the same as in the first embodiment.
And a third specific embodiment: the present embodiment differs from the first or second embodiment in that: in the first step, the ultrasonic power is 70 percent during ultrasonic cleaning.
Other steps are the same as those of the first or second embodiment.
The specific embodiment IV is as follows: one difference between this embodiment and the first to third embodiments is that: the ratio of the mass of the epoxy resin to the volume of the N, N-dimethylformamide solution in the step II was 2g: (8-10) mL.
Other steps are the same as those of the first to third embodiments.
Fifth embodiment: one to four differences between the present embodiment and the specific embodiment are: and in the second step, magnetic stirring is carried out at the temperature of 25-30 ℃ and the stirring speed of 300-400 r/min.
Other steps are the same as those of the first to fourth embodiments.
Specific embodiment six: the present embodiment differs from the first to fifth embodiments in that: the curing agent in the second step is one or two of anhydride curing agents methyl hexahydrophthalic anhydride and methyl tetrahydrophthalic anhydride.
Other steps are the same as those of the first to fifth embodiments.
Seventh embodiment: one difference between the present embodiment and the first to sixth embodiments is that: and step three, magnetically stirring for 5 to 6 hours at the temperature of 40 to 50 ℃ and at the stirring speed of 400 to 500 r/min.
Other steps are the same as those of embodiments one to six.
Eighth embodiment: one difference between the present embodiment and the first to seventh embodiments is that: in the fourth step, the pushing speed of the injector is 0.8-1 mm/min, the distance between the injector and the collecting device is 6-8 cm, positive pressure V+ =11-13 kV and negative pressure V- =11-13 kV are applied at the positions of the injector needle and the collecting device; the rotation speed of the collecting device is 100-120 r/min, the temperature is 20-25 ℃, and the humidity is 45-65%.
Other steps are the same as those of embodiments one to seven.
Detailed description nine: one of the differences between this embodiment and the first to eighth embodiments is: the concrete steps of gradient temperature curing in the step four are as follows: curing for 4-6 h at 80-100 ℃ and then curing for 4-6 h at 110-120 ℃.
Other steps are the same as those of embodiments one to eight.
Detailed description ten: the application of the epoxy resin composite medium with the high-heat-conductivity multilayer gradient structure in electronic packaging and/or electrical equipment is provided.
The following examples are used to verify the benefits of the present invention:
example 1: the preparation method of the epoxy resin composite medium with the high heat conduction multilayer gradient structure comprises the following steps:
step one: taking 10 5mL beakers, cleaning, drying, putting into a rotor with proper size, and labeling with filler content labels, wherein the labels are respectively marked as No. 1-10. 10 parts of 1mL of N, N-dimethylformamide solution are respectively measured and correspondingly added into No. 1-10 beakers, and 0g, 0.05g, 0.1g, 0.15g, 0.2g, 0.15g, 0.1g, 0.05g and 0g of hexagonal boron nitride (h-BN) are sequentially and accurately measured according to the mass of the added hexagonal boron nitride (h-BN), and are correspondingly added into No. 1-10 beakers, and magnetically stirred for 30min. Sequentially transferring the No. 1-10 beakers into an ultrasonic cleaner, and performing ultrasonic cleaning for 1h to uniformly disperse hexagonal boron nitride to obtain 10 groups of fillers, wherein the ultrasonic power is 70%.
Step two: 10 equal parts of a mixed solution consisting of 0.2g of epoxy resin (E-51) and 1mL of N, N-dimethylformamide are correspondingly added into 10 groups of fillers in the first step, magnetic stirring is carried out at the stirring speed of 300r/min at the temperature of 25 ℃, and the equal amounts of the curing agent methyl hexahydrophthalic anhydride and 2,4, 6-tris (dimethylaminomethyl) phenol are added into a No. 1-10 beaker while magnetic stirring, and after uniform mixing, 10 groups of epoxy resin mixed solution are obtained, wherein the volume ratio of the epoxy resin to the N, N-dimethylformamide solution to the curing agent to the 2,4, 6-tris (dimethylaminomethyl) phenol is 100:80:1.
step three: and (3) adding 0.2g of polycarbonate particles into the 10 groups of epoxy resin mixed solution in the step (II), and magnetically stirring at 50 ℃ and a stirring speed of 500r/min for 5 hours until the polycarbonate particles are completely dissolved to obtain 10 groups of epoxy resin/polycarbonate mixed solution spinning precursor liquid.
Step four: and (3) correspondingly extracting 1.2mL of 10 groups of epoxy resin/polycarbonate mixed solution spinning precursor liquid in the third step by using 10 5mL of injectors, carrying out electrostatic spinning by using a 21-gauge needle, sequentially carrying out electrostatic spinning on the 10 groups of epoxy resin/polycarbonate mixed solution spinning precursor liquid according to the sequence of 1-10 beakers, collecting the 10 groups of epoxy resin/polycarbonate mixed solution spinning precursor liquid on a roller to obtain a 10-layer integrated composite medium film with certain humidity, putting the 10-layer integrated composite medium film into a constant-temperature oven, curing the 10-layer integrated composite medium film at 100 ℃ for 4h, curing the 10-layer integrated composite medium film at 120 ℃ for 4h, and drying the 10-layer integrated composite medium film to obtain the high-heat-conductivity multilayer gradient structure epoxy resin composite medium with the thickness of 0.3mm.
In the fourth step, the pushing speed of the injector is 0.8mm/min, the distance between the injector and the collecting device is 8cm, positive pressure is applied to the positions of the needle of the injector and the collecting device at the same time, and negative pressure is V+ =12 kV, and V- =12 kV; the rotation speed of the collecting device is 100r/min, the temperature is 20 ℃, and the humidity is 45%.
Fig. 5 is a cross-sectional scanning electron microscope test chart of the epoxy resin composite medium with the high thermal conductivity multilayer gradient structure in example 1, fig. 6 is a line scanning energy spectrum of the element B at the cross section in fig. 5, and fig. 7 is a line scanning energy spectrum of the element N at the cross section in fig. 5. As shown in fig. 5, it can be seen that the thickness of the multi-layered gradient structure epoxy resin composite medium was 300 μm, and the difference in filler concentration of the inorganic filler in the horizontal direction was clearly observed. In order to better understand the distribution condition of inorganic filler in the polymer composite medium, the element line scanning energy spectrum characterization is carried out on the fracture surface of the film of the composite medium, and as BN filler is only added in the composite medium, the scanning detection object is B element and N element. As shown in fig. 6-7, the BN content is obviously increased and then decreased along the direction of the through plane, and the BN content is in a triangular symmetry shape, which is consistent with the expected result of the experiment, and the gradient structure distribution of the inorganic filler in the polymer composite medium is proved.
Example 2: the preparation method of the epoxy resin composite medium with the high heat conduction multilayer gradient structure comprises the following steps:
step one: taking 10 5mL beakers, cleaning, drying, putting into a rotor with proper size, and labeling with filler content labels, wherein the labels are respectively marked as No. 1-10. 10 parts of 1mL of N, N-dimethylformamide solution are respectively measured and correspondingly added into No. 1-10 beakers, and 0.075g, 0.0875g, 0.1g, 0.1125g, 0.125g, 0.1125g, 0.1g, 0.0875g and 0.075g of hexagonal boron nitride (h-BN) are sequentially added into No. 1-10 beakers, accurately weighed and correspondingly added into the beakers, and magnetically stirred for 30min. Sequentially transferring the No. 1-10 beakers into an ultrasonic cleaner, and performing ultrasonic cleaning for 1h to uniformly disperse hexagonal boron nitride to obtain 10 groups of fillers, wherein the ultrasonic power is 70%.
Step two: 10 equal parts of a mixed solution consisting of 0.2g of epoxy resin (E-51) and 1mL of N, N-dimethylformamide are correspondingly added into 10 groups of fillers in the first step, magnetic stirring is carried out at the stirring speed of 300r/min at the temperature of 25 ℃, and the equal amounts of the curing agent methyl hexahydrophthalic anhydride and 2,4, 6-tris (dimethylaminomethyl) phenol are added into a No. 1-10 beaker while magnetic stirring, and after uniform mixing, 10 groups of epoxy resin mixed solution are obtained, wherein the volume ratio of the epoxy resin to the N, N-dimethylformamide solution to the curing agent to the 2,4, 6-tris (dimethylaminomethyl) phenol is 100:80:1.
step three: and (3) adding 0.2g of polycarbonate particles into the 10 groups of epoxy resin mixed solution in the step (II), and magnetically stirring at 50 ℃ and a stirring speed of 500r/min for 5 hours until the polycarbonate particles are completely dissolved to obtain 10 groups of epoxy resin/polycarbonate mixed solution spinning precursor liquid.
Step four: and (3) correspondingly extracting 1.2mL of 10 groups of epoxy resin/polycarbonate mixed solution spinning precursor liquid in the third step by using 10 5mL of injectors, carrying out electrostatic spinning by using a 21-gauge needle, sequentially carrying out electrostatic spinning on the 10 groups of epoxy resin/polycarbonate mixed solution spinning precursor liquid according to the sequence of 1-10 beakers, collecting the 10 groups of epoxy resin/polycarbonate mixed solution spinning precursor liquid on a roller to obtain a 10-layer integrated composite medium film with certain humidity, putting the 10-layer integrated composite medium film into a constant-temperature oven, curing the 10-layer integrated composite medium film at 100 ℃ for 4h, curing the 10-layer integrated composite medium film at 120 ℃ for 4h, and drying the 10-layer integrated composite medium film to obtain the high-heat-conductivity multilayer gradient structure epoxy resin composite medium with the thickness of 0.3mm.
In the fourth step, the pushing speed of the injector is 0.8mm/min, the distance between the injector and the collecting device is 8cm, positive pressure is applied to the positions of the needle of the injector and the collecting device at the same time, and negative pressure is V+ =12 kV, and V- =12 kV; the rotation speed of the collecting device is 100r/min, the temperature is 20 ℃, and the humidity is 45%.
Fig. 8 is a cross-sectional scanning electron microscope test chart of the epoxy resin composite medium with the high thermal conductivity multilayer gradient structure in example 2, fig. 9 is a line scanning energy spectrum of the element B at the cross section in fig. 8, and fig. 10 is a line scanning energy spectrum of the element N at the cross section in fig. 8. In order to more clearly understand the distribution condition of inorganic filler in the polymer composite medium, the element line scanning energy spectrum characterization is carried out on the fracture surface of the film of the composite medium, and the scanning detection objects are B element and N element. The element line scanning structure is shown in fig. 9-10, and the BN content is obviously reduced and increased along the film penetrating direction, and is in inverted triangle symmetry, consistent with experimental expectation and SEM image, and the gradient structure distribution of the inorganic filler in the polymer composite medium is proved.
Comparative example 1: the preparation method of the epoxy resin composite film comprises the following steps:
1. according to 2g: a10 mL ratio was measured by weighing 2g of epoxy resin (E-51) and 10mL of N, N-dimethylformamide.
2. A25 mL beaker was cleaned and dried and placed in a rotor of appropriate size. Pouring epoxy resin (E-51) and N, N-dimethylformamide in the first step into a 25mL beaker, stirring at the stirring speed of 300r/min by using a magnetic stirrer, and sequentially adding a curing agent (methyl hexahydrophthalic anhydride) and 2,4, 6-tris (dimethylaminomethyl) phenol in the stirring process to obtain a mixed solution; the total volume of the epoxy resin and the N, N-dimethylformamide solution, the curing agent (methyl hexahydrophthalic anhydride) and 2,4, 6-tris (dimethylaminomethyl) phenol were set to 100:80:1.
3. And (3) continuously adding 2g of polycarbonate particles into the mixed solution obtained in the step (II), and magnetically stirring at the stirring speed of 500r/min for 5 hours at the temperature of 50 ℃ by using a magnetic stirrer to obtain the spinning precursor solution of the mixed solution of the epoxy resin and the polycarbonate.
4. The method adopts electrostatic spinning: extracting the spinning precursor solution of the mixed solution of the epoxy resin and the polycarbonate prepared in the step three by using a syringe, extracting 7mL of the spinning precursor solution of the mixed solution of the epoxy resin and the polycarbonate by using a 10mL syringe, setting the advancing speed of the syringe on a spinning machine to be 0.8mm/min by using a 21-gauge needle, setting the distance between the syringe and a collecting device to be 8cm, and simultaneously applying positive pressure V+ =12 kV and negative pressure V- =12 kV at the positions of the syringe needle and the collecting device; the rotation speed of the collecting device is 100r/min, the temperature is 20 ℃, and the humidity is 45%; the film with certain humidity is collected on a roller, and is put into a constant temperature oven, and is cured for 4 hours at 100 ℃ and then is cured for 4 hours at 120 ℃ and is dried, so that the epoxy resin composite film with the thickness of 0.3mm is obtained.
FIG. 1 is a cross-sectional scanning electron microscope test chart of an epoxy resin composite film in comparative example 1; SEM characterization is carried out on the epoxy resin composite film in comparative example 1, and the characterization result is shown in figure 1, so that the fracture surface of the epoxy resin composite film can be seen to be river-like, and is a typical brittle material fracture morphology.
Comparative example 2: a preparation method of a single-layer uniform epoxy resin composite medium comprises the following steps:
1. a25 mL beaker is taken, cleaned and dried, the beaker is put into a rotor with proper size, 10mL of N, N-dimethylformamide is respectively measured and added into the beaker, 1g of hexagonal boron nitride (h-BN) is accurately weighed and added into the beaker, and magnetic stirring is carried out for 30 minutes.
2. Transferring the beaker in the first step into an ultrasonic cleaner for ultrasonic treatment for 1h, wherein the ultrasonic power is 70%, so that the hexagonal boron nitride is uniformly dispersed.
3. According to 2g: a10 mL ratio was measured by weighing 2g of epoxy resin (E-51) and 10mL of N, N-dimethylformamide.
4. Pouring the epoxy resin (E-51) and N, N-dimethylformamide in the step three into a 25mL beaker, and sequentially adding a curing agent (methyl hexahydrophthalic anhydride) and 2,4, 6-tris (dimethylaminomethyl) phenol in the stirring process at the stirring speed of 300r/min and the stirring temperature of 25 ℃ by using a magnetic stirrer according to the following ratio of 100:80:1.
5. Continuing adding the mixed solution obtained in the step four into the epoxy resin 1:1 proportion of 2g of polycarbonate particles, and magnetically stirring the mixture at 50 ℃ for 5 hours at a stirring speed of 500r/min by using a magnetic stirrer to prepare a spinning precursor solution of an epoxy resin and polycarbonate mixed solution.
6. The method adopts electrostatic spinning: and (3) extracting the spinning precursor solution of the epoxy resin and polycarbonate mixed solution prepared in the step (V) by using an injector, extracting 4mL of the spinning precursor solution of the epoxy resin and polycarbonate mixed solution by using a 5mL injector, setting the advancing speed of the injector on a spinning machine to be 0.8mm/min by using a 21-gauge needle, wherein the distance between the injector and a collecting device is 8cm, the positive and negative voltages applied at the needle and the collecting device are V+ =12 kV, V- =12 kV, the rotating speed of the collecting device is 100r/min, the temperature is 20 ℃, and the humidity is 45%. The film with certain humidity is collected on a roller, and is put into a constant temperature oven, and is firstly cured for 4 hours at 100 ℃ and then cured for 4 hours at 120 ℃, and is dried, so that the single-layer uniform epoxy resin composite medium with the thickness of 0.3mm is obtained.
Fig. 2 is a cross-sectional scanning electron microscope test chart of a single-layer uniform epoxy resin composite medium in comparative example 2, fig. 3 is a line scanning energy spectrum of B element at a scribe line in fig. 2, and fig. 4 is a line scanning energy spectrum of N element at a scribe line in fig. 2, as shown in fig. 2, the thickness of the epoxy resin composite medium is 300 μm, and no obvious faults, voids, and crack defects are observed. In order to further observe the dispersion of the inorganic filler in the polymer, the entire fracture surface has an h-BN distribution as shown in FIGS. 3 to 4, and the distribution is uniform.
The thermal conductivities of the single-layer uniform epoxy resin composite medium and the epoxy resin composite medium with a multi-layer gradient structure of the final product obtained after the curing of the examples 1-2 and the comparative examples 1-2 are shown in the table 1 (data measured by a laser flash method); table 1 shows the thermal conductivities of the epoxy resin composite films obtained in examples 1-2 and comparative examples 1-2;
TABLE 1
| Material | Thermal conductivity (W/mK) | Breakdown strength (kV/mm) |
| Example 1 high thermal conductivity multilayer gradient structured epoxy resin composite Medium | 0.42 | 106.5 |
| Example 2 high thermal conductivity multilayer gradient structured epoxy resin composite Medium | 0.38 | 110.1 |
| Comparative example 1 epoxy resin composite film | 0.18 | 53 |
| Comparative example 2 Single layer homogeneous epoxy resin composite media | 0.33 | 40 |
As shown in Table 1, the thermal conductivity of the epoxy resin composite medium with the high thermal conductivity multi-layer gradient structure in the embodiment 1 reaches 0.42W/m.K, which is improved by 0.04W/m.K compared with the 0.38W/m.K of the epoxy resin composite medium with the high thermal conductivity multi-layer gradient structure in the embodiment 2, and is improved by 0.09W/m.K compared with the 0.33W/m.K of the epoxy resin composite medium with the single-layer uniform structure in the embodiment 2, the difference of the thermal conductivity is considered to be the difference of the thermal conductivity of different filling materials among adjacent layers, so that the difference of the thermal conduction paths in the direction of a penetrating plane is caused, and the multi-layer gradient structure in the embodiment 1 is easier to form a continuous and effective thermal conduction path compared with the multi-layer gradient composite medium in the embodiment 2, thereby achieving the effect of promoting the effective phonon transmission and further improving the thermal conductivity of the composite medium.
Fig. 11 is a breakdown characteristic diagram of each of the epoxy resin composite media of examples 1-2 and comparative examples 1-2, ■ shows the epoxy resin composite film of comparative example 1, +..
As shown in fig. 11, the breakdown strength of the single-layer uniform epoxy resin composite medium of comparative example 2 is reduced compared to that of the epoxy resin composite film of comparative example 1, and the breakdown strength is reduced due to the fact that the viscosity of the uncured mixture is necessarily increased by filling only boron nitride; in addition, due to the high dielectric constant of the filler, free charges in the medium are increased, and a conductive path is inevitably formed, so that breakdown strength is reduced.
In the embodiment 1, the doped filler is in gradient distribution in the polymer matrix, so that the electric field in the composite medium is optimally distributed, and the formation of a conductive path is inhibited, so that the breakdown strength of the composite medium is improved. Another reason is that the inorganic filler content increases and decreases after the inorganic filler content decreases in the through plane direction, and the irregular distribution of the filler caused by the difference of the filler concentration between each layer increases the tortuosity of an electric path, is a main reason for inhibiting the injection and transportation of carriers and blocking the passage of electron transmission, and also improves the breakdown strength of the multilayer gradient epoxy resin composite medium.
Fig. 12 is a graph showing dielectric properties of each of the epoxy resin composite media of examples 1-2 and comparative examples 1-2, ■ showing the epoxy resin composite film of comparative example 1, +..
As shown in fig. 12, the introduction of the h-BN filler increased the relative permittivity of the polymer composite medium, and the single-layer uniform epoxy resin composite medium of comparative example 2 had the highest permittivity, which was mainly attributed to the intrinsically high permittivity of boron nitride, and another reason was that the addition of the thermally conductive filler caused a large number of interface defects between the filler and the filler, and between the filler and the matrix, and the composite material had increased interfacial polarization and increased permittivity.
From the graph, it can be observed that the dielectric constant of the epoxy resin composite medium of the multi-layer gradient structure of examples 1-2 is reduced compared with that of the single-layer uniform composite medium of comparative example 2. The dielectric constant is the capacity of the dielectric material to hold charges, and the decrease of the relative dielectric constant is probably due to the fact that the filler is arranged in a mode of increasing firstly and then decreasing in the direction of penetrating the plane, so that an electron transmission path can be greatly blocked, the tortuosity of an electric path is increased, and the charges in the polymer composite medium are reduced, so that the dielectric constant of the composite medium is reduced; another reason is the gradient distribution of the filler, which reduces the interface defects between the filler and the filler, and reduces the interface polarization, resulting in a multilayer structure with a slightly lower relative dielectric constant than the single layer homogeneous composite medium of comparative example 2.
Fig. 13 is a dielectric loss image of each of the epoxy resin composite media of examples 1-2 and comparative examples 1-2, ■ showing the epoxy resin composite film of comparative example 1, +..
As shown in fig. 13, it can be observed that the loss tangent of the single-layer uniform epoxy resin composite medium of comparative example 2 is higher than that of the epoxy resin composite film of comparative example 1, which is probably due to the addition of h-BN, which inevitably forms a conductive path in the polymer composite medium, promotes movement of carriers, increases the conduction loss, and thus increases the loss tangent of the composite medium. The multilayer composite medium of examples 1-2 has a reduced dielectric loss compared to the single-layer homogeneous composite medium of comparative example 2 because of the gradient distribution of the filler in the multilayer structure, which increases the tortuosity of the electrical path due to irregular distribution of the filler in the matrix, inhibits carrier injection and transport, and results in reduced conduction loss, thereby achieving a reduction in dielectric loss.
Claims (5)
1. The preparation method of the epoxy resin composite medium with the high heat conduction multilayer gradient structure is characterized by comprising the following steps of:
step one: 10 parts of N, N-dimethylformamide solution with the same volume is correspondingly added into a No. 1-10 container, 10 parts of hexagonal boron nitride is additionally taken, and the mass ratio of the added hexagonal boron nitride is 0:2:4:6:8:8:6:4:2:0 or 3:3.5:4:4.5:5:5:4.5:4:3.5:3 are added into a No. 1-10 container in sequence, and after magnetic stirring for 30-50 min, ultrasonic cleaning is carried out for 40-60 min to obtain 10 groups of fillers;
the ratio of the total mass of hexagonal boron nitride to the volume of the N, N-dimethylformamide solution in each set of containers in step one was 1g: (0.8-1) mL;
step two: 10 equal parts of epoxy resin and N, N-dimethylformamide are combined into a mixed solution, the mixed solution is correspondingly added into 10 groups of fillers in the first step, and an equal amount of curing agent and 2,4, 6-tris (dimethylaminomethyl) phenol are added into a No. 1-10 container while magnetic stirring, and after uniform mixing, 10 groups of epoxy resin mixed solution are obtained, wherein the ratio of the mass of the epoxy resin, the volume of the curing agent and the volume of the 2,4, 6-tris (dimethylaminomethyl) phenol is (100-120 g): (80-100) mL:1 mL; the volume of the curing agent added to each container is equal, and the volume of the 2,4, 6-tris (dimethylaminomethyl) phenol added to each container is equal;
the ratio of the mass of the epoxy resin to the volume of the N, N-dimethylformamide solution in the step II was 2g: (8-10) mL;
step three: adding equal amount of polycarbonate particles into the 10 groups of epoxy resin mixed solution in the second step, and magnetically stirring until the polycarbonate particles are completely dissolved to obtain 10 groups of epoxy resin/polycarbonate mixed solution spinning precursor liquid; the mass of the polycarbonate particles added into each group of epoxy resin mixed solution is equal;
the total mass of hexagonal boron nitride, mass ratio of each part of epoxy resin to each part of polycarbonate particles is 1:0.2:0.2;
step four: and (3) correspondingly extracting 10 groups of epoxy resin/polycarbonate mixed solution spinning precursor solutions in the third step by using 10 injectors, sequentially carrying out electrostatic spinning on the 10 groups of epoxy resin/polycarbonate mixed solution spinning precursor solutions according to the sequence of No. 1-10 containers to obtain 10 layers of integrated composite medium films, curing the 10 layers of integrated composite medium films at 80-100 ℃ for 4-6 hours, curing the 10 layers of integrated composite medium films at 110-120 ℃ for 4-6 hours, and drying to obtain the high-heat-conductivity multi-layer gradient structure epoxy resin composite medium.
2. The method for preparing the epoxy resin composite medium with the high-heat-conductivity multilayer gradient structure according to claim 1, wherein in the second step, magnetic stirring is performed at the stirring speed of 300-400 r/min at the temperature of 25-30 ℃.
3. The method for preparing the epoxy resin composite medium with the high-heat-conductivity multilayer gradient structure according to claim 1, wherein the curing agent in the second step is one or two of methyl hexahydrophthalic anhydride and methyl tetrahydrophthalic anhydride.
4. The preparation method of the epoxy resin composite medium with the high-heat-conductivity multilayer gradient structure, which is disclosed in claim 1, is characterized in that in the third step, magnetic stirring is carried out for 5-6 hours at the stirring speed of 400-500 r/min at the temperature of 40-50 ℃.
5. The preparation method of the epoxy resin composite medium with the high-heat-conductivity multilayer gradient structure, which is disclosed in claim 1, is characterized in that in the fourth step, the advancing speed of an injector is 0.8-1 mm/min, the distance between the injector and a collecting device is 6-8 cm, positive pressure is applied to the needle of the injector at a position of V+ = 11-13 kV, and negative pressure is applied to the collecting device at a position of V- = -11-13 kV; the rotation speed of the collecting device is 100-120 r/min, the temperature is 20-25 ℃, and the humidity is 45-65%.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202310285867.5A CN116288944B (en) | 2023-03-21 | 2023-03-21 | Preparation method and application of high-heat-conductivity multi-layer gradient structure epoxy resin composite medium |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202310285867.5A CN116288944B (en) | 2023-03-21 | 2023-03-21 | Preparation method and application of high-heat-conductivity multi-layer gradient structure epoxy resin composite medium |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN116288944A CN116288944A (en) | 2023-06-23 |
| CN116288944B true CN116288944B (en) | 2023-11-28 |
Family
ID=86814741
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202310285867.5A Active CN116288944B (en) | 2023-03-21 | 2023-03-21 | Preparation method and application of high-heat-conductivity multi-layer gradient structure epoxy resin composite medium |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN116288944B (en) |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103122075A (en) * | 2013-03-19 | 2013-05-29 | 苏州格瑞丰纳米科技有限公司 | High heat-conducting thin graphene-based composite material, as well as preparation method and application thereof |
| CN104046823A (en) * | 2014-06-13 | 2014-09-17 | 上海和辉光电有限公司 | Graded metal-ceramic composite and preparation method thereof |
| WO2015084951A1 (en) * | 2013-12-04 | 2015-06-11 | Cornell University | Ceramic-polymer hybrid nanostructures, methods for producing and applications thereof |
| CN109972398A (en) * | 2019-04-16 | 2019-07-05 | 清华大学 | A kind of high thermal conductivity flexible-epoxy insulating materials and the preparation method and application thereof |
| CN110016723A (en) * | 2019-04-08 | 2019-07-16 | 深圳先进技术研究院 | A kind of dielectric composite material, preparation method and plate capacitor |
| CN110318690A (en) * | 2019-05-09 | 2019-10-11 | 中国地质大学（北京） | A kind of shaped wear-resistant belt of drill pipe joint and preparation method thereof |
| CN110951254A (en) * | 2019-11-24 | 2020-04-03 | 上海大学 | Boron nitride composite high-thermal-conductivity insulating polymer composite material and preparation method thereof |
-
2023
- 2023-03-21 CN CN202310285867.5A patent/CN116288944B/en active Active
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103122075A (en) * | 2013-03-19 | 2013-05-29 | 苏州格瑞丰纳米科技有限公司 | High heat-conducting thin graphene-based composite material, as well as preparation method and application thereof |
| WO2015084951A1 (en) * | 2013-12-04 | 2015-06-11 | Cornell University | Ceramic-polymer hybrid nanostructures, methods for producing and applications thereof |
| CN104046823A (en) * | 2014-06-13 | 2014-09-17 | 上海和辉光电有限公司 | Graded metal-ceramic composite and preparation method thereof |
| CN110016723A (en) * | 2019-04-08 | 2019-07-16 | 深圳先进技术研究院 | A kind of dielectric composite material, preparation method and plate capacitor |
| CN109972398A (en) * | 2019-04-16 | 2019-07-05 | 清华大学 | A kind of high thermal conductivity flexible-epoxy insulating materials and the preparation method and application thereof |
| CN110318690A (en) * | 2019-05-09 | 2019-10-11 | 中国地质大学（北京） | A kind of shaped wear-resistant belt of drill pipe joint and preparation method thereof |
| CN110951254A (en) * | 2019-11-24 | 2020-04-03 | 上海大学 | Boron nitride composite high-thermal-conductivity insulating polymer composite material and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN116288944A (en) | 2023-06-23 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Zhao et al. | A critical review of the preparation strategies of thermally conductive and electrically insulating polymeric materials and their applications in heat dissipation of electronic devices | |
| Yao et al. | Nano-BN encapsulated micro-AlN as fillers for epoxy composites with high thermal conductivity and sufficient dielectric breakdown strength | |
| CN109913185B (en) | Multilayer structure heat-conducting composite material containing heat-conducting film and preparation method thereof | |
| Wang et al. | Sandwiched epoxy–alumina composites with synergistically enhanced thermal conductivity and breakdown strength | |
| Zhang et al. | Achieving high-efficiency and robust 3D thermally conductive while electrically insulating hybrid filler network with high orientation and ordered distribution | |
| CN101899209B (en) | Heat conductive insulation material and preparation method thereof | |
| CN101225231B (en) | Insulating heat-conductive glass-fiber reinforced PPS composite material and preparation method thereof | |
| CN102070899B (en) | Insulating and heat-conducting polyamide composite material and preparation method thereof | |
| Wang et al. | Advances in polymers and composite dielectrics for thermal transport and high-temperature applications | |
| CN109972398B (en) | High-thermal-conductivity flexible epoxy resin insulating material and preparation method and application thereof | |
| CN102558863A (en) | Low-dielectric-property polyphenylene sulphide composite material and preparation method thereof | |
| CN113881190A (en) | Epoxy resin composite material for packaging power electronic transformer and preparation method thereof | |
| Zhou et al. | Effect of coupling agents on the dielectric properties of aluminum particles reinforced epoxy resin composites | |
| BRPI0722152A2 (en) | POLYMERIC CONCRETE ELECTRIC INSULATION SYSTEM | |
| CN115044041B (en) | Preparation method of polyimide-based modified boron nitride nanosheet heat-conducting composite material | |
| CN116288944B (en) | Preparation method and application of high-heat-conductivity multi-layer gradient structure epoxy resin composite medium | |
| Zhang et al. | Cyanate ester composites containing surface functionalized BN particles with grafted hyperpolyarylamide exhibiting desirable thermal conductivities and a low dielectric constant | |
| Tian et al. | Enhanced thermal conductivity and rheological performance of epoxy and liquid crystal epoxy composites with filled Al2O3 compound | |
| CN102533228A (en) | Coated heat conducting material, heat conducting composite material and preparing methods thereof | |
| CN101914255B (en) | High-temperature resistant polyphenylene sulfide composite material with low dielectric constant and preparation method thereof | |
| CN115216087A (en) | Preparation, forming method and application of novel low-thermal expansion coefficient and low-dielectric composite material | |
| Wang et al. | Isotropical conductive adhesives with very-long silver nanowires as conductive fillers | |
| Sima et al. | Cactus-like double-oriented magnetic SiC and BN networks leading to simultaneously enhanced dielectric strength and thermal conductivity of epoxy composites | |
| Di-wu et al. | Synergetic improvements of intrinsic thermal conductivity and breakdown strength in liquid crystal epoxy resin for high voltage applications | |
| Na et al. | Synthesis of a novel biphenyl epoxy resin and its hybrid composite with high thermal conductivity |
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 | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |