CN110452418B - High-thermal-conductivity polyimide film prepared from core-shell structure heat-conducting filler and preparation method thereof - Google Patents
High-thermal-conductivity polyimide film prepared from core-shell structure heat-conducting filler and preparation method thereof Download PDFInfo
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- 229920001721 polyimide Polymers 0.000 title claims abstract description 55
- 239000000945 filler Substances 0.000 title claims abstract description 49
- 239000011258 core-shell material Substances 0.000 title claims abstract description 42
- 238000002360 preparation method Methods 0.000 title claims abstract description 25
- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 claims abstract description 103
- 229910052582 BN Inorganic materials 0.000 claims abstract description 82
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 56
- 229920005575 poly(amic acid) Polymers 0.000 claims abstract description 26
- 238000000034 method Methods 0.000 claims abstract description 15
- 239000011231 conductive filler Substances 0.000 claims abstract description 14
- 239000003607 modifier Substances 0.000 claims abstract description 7
- 238000001354 calcination Methods 0.000 claims abstract description 6
- 238000000707 layer-by-layer assembly Methods 0.000 claims abstract description 6
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims abstract 3
- 229910052796 boron Inorganic materials 0.000 claims abstract 3
- 238000005121 nitriding Methods 0.000 claims abstract 2
- 239000007788 liquid Substances 0.000 claims description 26
- 239000006185 dispersion Substances 0.000 claims description 25
- 238000003756 stirring Methods 0.000 claims description 19
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 16
- 239000008367 deionised water Substances 0.000 claims description 12
- 229910021641 deionized water Inorganic materials 0.000 claims description 12
- 238000001035 drying Methods 0.000 claims description 10
- 238000010438 heat treatment Methods 0.000 claims description 10
- 150000004985 diamines Chemical class 0.000 claims description 9
- 150000008064 anhydrides Chemical class 0.000 claims description 8
- VLDPXPPHXDGHEW-UHFFFAOYSA-N 1-chloro-2-dichlorophosphoryloxybenzene Chemical compound ClC1=CC=CC=C1OP(Cl)(Cl)=O VLDPXPPHXDGHEW-UHFFFAOYSA-N 0.000 claims description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 7
- 238000001816 cooling Methods 0.000 claims description 7
- GTDPSWPPOUPBNX-UHFFFAOYSA-N ac1mqpva Chemical compound CC12C(=O)OC(=O)C1(C)C1(C)C2(C)C(=O)OC1=O GTDPSWPPOUPBNX-UHFFFAOYSA-N 0.000 claims description 5
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 4
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 4
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 4
- 239000000463 material Substances 0.000 claims description 4
- 239000003960 organic solvent Substances 0.000 claims description 4
- 239000002245 particle Substances 0.000 claims description 4
- 239000002994 raw material Substances 0.000 claims description 4
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 3
- WZCQRUWWHSTZEM-UHFFFAOYSA-N 1,3-phenylenediamine Chemical compound NC1=CC=CC(N)=C1 WZCQRUWWHSTZEM-UHFFFAOYSA-N 0.000 claims description 2
- CBCKQZAAMUWICA-UHFFFAOYSA-N 1,4-phenylenediamine Chemical group NC1=CC=C(N)C=C1 CBCKQZAAMUWICA-UHFFFAOYSA-N 0.000 claims description 2
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- ISKQADXMHQSTHK-UHFFFAOYSA-N [4-(aminomethyl)phenyl]methanamine Chemical compound NCC1=CC=C(CN)C=C1 ISKQADXMHQSTHK-UHFFFAOYSA-N 0.000 claims description 2
- 229940018564 m-phenylenediamine Drugs 0.000 claims description 2
- 125000006160 pyromellitic dianhydride group Chemical group 0.000 claims description 2
- 150000001412 amines Chemical class 0.000 claims 2
- LZDHIQDKAYUDND-UHFFFAOYSA-N biphenylene-1,2-diamine Chemical compound C1=CC=C2C3=C(N)C(N)=CC=C3C2=C1 LZDHIQDKAYUDND-UHFFFAOYSA-N 0.000 claims 1
- 150000004767 nitrides Chemical class 0.000 claims 1
- 238000002525 ultrasonication Methods 0.000 claims 1
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- 239000002253 acid Substances 0.000 description 3
- 238000001000 micrograph Methods 0.000 description 3
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical group O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 3
- 229920002647 polyamide Polymers 0.000 description 3
- HLBLWEWZXPIGSM-UHFFFAOYSA-N 4-Aminophenyl ether Chemical compound C1=CC(N)=CC=C1OC1=CC=C(N)C=C1 HLBLWEWZXPIGSM-UHFFFAOYSA-N 0.000 description 2
- JVERADGGGBYHNP-UHFFFAOYSA-N 5-phenylbenzene-1,2,3,4-tetracarboxylic acid Chemical compound OC(=O)C1=C(C(O)=O)C(C(=O)O)=CC(C=2C=CC=CC=2)=C1C(O)=O JVERADGGGBYHNP-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 229960000583 acetic acid Drugs 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 239000004020 conductor Substances 0.000 description 2
- 239000012362 glacial acetic acid Substances 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
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- 239000004005 microsphere Substances 0.000 description 2
- UDQLIWBWHVOIIF-UHFFFAOYSA-N 3-phenylbenzene-1,2-diamine Chemical compound NC1=CC=CC(C=2C=CC=CC=2)=C1N UDQLIWBWHVOIIF-UHFFFAOYSA-N 0.000 description 1
- VQVIHDPBMFABCQ-UHFFFAOYSA-N 5-(1,3-dioxo-2-benzofuran-5-carbonyl)-2-benzofuran-1,3-dione Chemical compound C1=C2C(=O)OC(=O)C2=CC(C(C=2C=C3C(=O)OC(=O)C3=CC=2)=O)=C1 VQVIHDPBMFABCQ-UHFFFAOYSA-N 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
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- 229910052593 corundum Inorganic materials 0.000 description 1
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- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- ZZTCPWRAHWXWCH-UHFFFAOYSA-N diphenylmethanediamine Chemical compound C=1C=CC=CC=1C(N)(N)C1=CC=CC=C1 ZZTCPWRAHWXWCH-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000004100 electronic packaging Methods 0.000 description 1
- 229910021389 graphene Inorganic materials 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
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- RUDCBGCNXOSCTI-UHFFFAOYSA-N n-methoxy-4-[4-(methoxyamino)phenyl]aniline Chemical compound C1=CC(NOC)=CC=C1C1=CC=C(NOC)C=C1 RUDCBGCNXOSCTI-UHFFFAOYSA-N 0.000 description 1
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- 229910001845 yogo sapphire Inorganic materials 0.000 description 1
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- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/38—Boron-containing compounds
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K7/00—Use of ingredients characterised by shape
- C08K7/16—Solid spheres
- C08K7/18—Solid spheres inorganic
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K9/00—Use of pretreated ingredients
- C08K9/04—Ingredients treated with organic substances
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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- C08J2379/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen, or carbon only, not provided for in groups C08J2361/00 - C08J2377/00
- C08J2379/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
- C08J2379/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
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- C08K3/38—Boron-containing compounds
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- C08K2003/385—Binary compounds of nitrogen with boron
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Abstract
本发明公开了一种核壳结构导热填料制备的高导热聚酰亚胺薄膜及其制备方法，导热填料为核壳结构的导热填料；薄膜包括10‑50质量份的导热填料，1‑5质量份的改性剂，80‑500质量份的聚酰胺酸溶液，导热填料为氮化硼包覆氧化铝的核壳导热填料；核壳导热填料是通过改性剂处理氧化铝和高温煅烧氮化硼，采用静电自组装方法来制备而得，将核壳导热填料加入聚酰胺酸溶液中搅拌混合均匀，真空静置消泡后，铺设成薄膜，程序升温热亚胺化，制得高导热聚酰亚胺薄膜。该薄膜具有高导热系数和电绝缘的主要特性，且加工成本较低，制备工艺简单，且成型周期短，在电子、航空航天、机械领域都有广泛的应用前景。
The invention discloses a high thermal conductivity polyimide film prepared by a core-shell structure heat-conducting filler and a preparation method thereof. The heat-conducting filler is a core-shell structure heat-conducting filler; parts of modifier, 80-500 parts by mass of polyamic acid solution, and the thermally conductive filler is a core-shell thermally conductive filler of boron nitride-coated alumina; the core-shell thermally conductive filler is processed by modifying the alumina and calcining and nitriding at high temperature. Boron is prepared by electrostatic self-assembly method. The core-shell thermal conductive filler is added into the polyamic acid solution, stirred and mixed evenly. Imide film. The film has the main characteristics of high thermal conductivity and electrical insulation, low processing cost, simple preparation process, and short molding cycle, and has broad application prospects in the fields of electronics, aerospace and machinery.
Description
Technical Field
The invention belongs to the technical field of polyimide films, and particularly relates to a high-thermal-conductivity polyimide film prepared from a core-shell structure thermal-conductive filler and a preparation method thereof.
Background
With the rapid development of science and technology, particularly in the electronic field, rising science and technology is a new and advanced science and technology, electronic elements are developed towards miniaturization and integration, so that the density of the electronic elements is increased, the heat dissipation problem is increasingly serious, and the efficiency, the safety and the service life of electronic equipment are influenced. Polyimide film, a high molecular material with good thermal and mechanical properties, in particular, it has low dielectric constant and loss tangent, high thermal stability and storage modulus, and is widely used in electronic packaging materials. However, the pure polyimide film has an intrinsic thermal conductivity of only about 0.1W/(m · K), and is not a heat conductive material, and thus cannot be practically used.
Boron nitride, a two-dimensional material, is a hexagonal boron nitride having a layered structure similar to graphite, is called "white graphene" due to its atomically flat and electrically insulating surface, relatively low density and low price, and has not only high thermal conductivity (about 600W/(m · K)) in the planar direction but also excellent electrical insulation. Boron nitride is used as a heat-conducting filler, a good heat-conducting network can be constructed, the heat-conducting coefficient of the polyimide film can be improved by adding pure boron nitride, the polyimide heat-conducting film is prepared by modifying boron nitride in the patent CN 109627472A, but the cost is very high due to the overlarge proportion of the boron nitride, and an effective heat-conducting channel is not formed in the polyimide substrate; in the same patent CN 106243715B, boron nitride and polyimide microspheres are used to prepare polyimide heat conducting materials, but the process cost is complex and polyimide microspheres need to be prepared. Therefore, in terms of polyimide thermal conductive films, the efficient increase of thermal conductivity and the reduction of cost in the film process are two difficult problems to be solved.
At present, the heat conduction coefficient of the heat conduction material is generally improved by two modes, one mode is to add a filler with high heat conduction coefficient and innovate the mode and the effect of constructing a heat conduction channel; the other is to reduce the interface scattering of phonons by improving the compatibility of the matrix and the filler. When the heat-conducting filler with the core-shell structure is added into the matrix, the matrix and the shell heat-conducting filler act synergistically, an effective heat-conducting channel can be constructed, a three-dimensional network structure is formed in the polyimide, and phonons can be rapidly transmitted; and when the heat-conducting filler takes the alumina as the core, the comprehensive cost price is lower. In conclusion, the core-shell heat-conducting filler and the heat-conducting filler are cooperated to construct the heat-conducting network structure, so that the polyimide film with high heat conductivity and low cost is prepared.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides a high-thermal-conductivity polyimide film prepared from a core-shell structure thermal-conductivity filler and a preparation method thereof. The film has the main characteristics of high heat conductivity coefficient and electric insulation, and has the characteristics of lower processing cost, simple preparation process and short forming period.
The technical scheme for realizing the invention is as follows:
the core-shell structure heat-conducting filler is boron nitride coated alumina prepared by treating alumina with a modifier and calcining boron nitride at high temperature and adopting an electrostatic self-assembly method.
The alumina is spherical and has a particle size of 1-30 um; the boron nitride is hexagonal boron nitride and has a particle size of 50nm-5 um.
The preparation method of the heat-conducting filler comprises the following steps:
(1) preparation of KH550 modified alumina: preparing a dispersion liquid by using absolute ethyl alcohol and deionized water, wherein the mass concentration of the absolute ethyl alcohol is 5-60%, adjusting the pH value to be 5-6, and slowly dripping KH550 into the dispersion liquid, wherein the mass part of the KH550 is 1-5% of the dispersion liquid; stirring for hydrolysis, adding alumina, wherein the mass part of the alumina is 10-60% of the dispersion liquid, heating in a water bath, and then centrifugally drying to obtain KH550 modified alumina;
2) preparing modified boron nitride: weighing boron nitride, calcining for 1-2h in the environment of 900-1200 ℃, using deionized water as a dispersion liquid, performing ultrasonic treatment, and performing centrifugal drying to prepare modified boron nitride;
3) preparing boron nitride coated alumina: according to the mass ratio of the modified boron nitride to the modified alumina of 1: 1-10, weighing the modified boron nitride prepared in the step (2), adding deionized water, preparing boron nitride dispersion liquid with the concentration of 1-10mg/ml, adjusting the pH to 4-5 after ultrasonic treatment, adding the KH550 modified alumina prepared in the step (1), stirring, centrifuging and drying to prepare the boron nitride coated alumina core-shell heat-conducting filler.
A high-thermal-conductivity polyimide film prepared from core-shell structure thermal-conductivity filler is prepared from the following raw materials in parts by mass, 10-50 parts by mass of thermal-conductivity filler, 1-5 parts by mass of modifier and 80-500 parts by mass of polyamic acid solution;
the heat-conducting filler is a core-shell structure heat-conducting filler.
The modifier is a silane coupling agent KH 550.
The polyamic acid solution is prepared by dissolving diamine in an organic solvent and then adding dibasic anhydride into the diamine solution; the mass ratio of the dibasic anhydride to the diamine is 1: 1-1.05, and the mass concentration of the polyamic acid solution is 15-25%.
The binary anhydride is pyromellitic dianhydride (PMDA) and 3, 3，，4，4，Biphenyltetracarboxylic dianhydride, 2, 3，，3，4，Biphenyltetracarboxylic dianhydride, 3，，4，4，Benzophenone tetracarboxylic dianhydride, 2, 3，，6，7，-one of naphthalene tetracarboxylic dianhydrides;
the diamine is p-phenylenediamine, m-phenylenediamine, biphenyldiamine, 4，Diaminodiphenyl ether, p-xylylenediamine, 3, 4，Diaminodiphenyl ether, 4，Diaminodiphenylmethane, 3，-one of dimethoxybenzidine;
the organic solvent is one of N, N-dimethylacetamide, N-dimethylformamide, N-methylpyrrolidone, dimethylacetamide and dimethyl sulfoxide.
The thickness of the film is 10-500 um.
A preparation method of a high-thermal-conductivity polyimide film prepared from core-shell structure thermal-conductivity filler comprises the following steps:
1) preparation of KH550 modified alumina: preparing a dispersion liquid by using absolute ethyl alcohol and deionized water, wherein the mass concentration of the absolute ethyl alcohol is 5-60%, adjusting the pH value to be 5-6, and slowly dripping KH550 into the dispersion liquid, wherein the mass part of the KH550 is 1-5% of the dispersion liquid; stirring for hydrolysis, adding alumina, wherein the mass part of the alumina is 10-60% of the dispersion liquid, heating in a water bath, and then centrifugally drying to obtain KH550 modified alumina;
2) preparing modified boron nitride: weighing boron nitride, calcining for 1-2h in the environment of 900-1200 ℃, using deionized water as a dispersion liquid, performing ultrasonic treatment, and performing centrifugal drying to prepare modified boron nitride;
3) preparing boron nitride coated alumina: weighing the modified boron nitride prepared in the step 2), adding deionized water, preparing a boron nitride dispersion liquid, adjusting the pH to 4-5 after ultrasonic treatment, adding the KH550 modified alumina prepared in the step 1), stirring, centrifuging and drying to prepare a core-shell heat-conducting filler of boron nitride coated alumina;
4) after boron nitride is uniformly dispersed in the organic dispersion liquid, adding diamine for dissolving, and then adding dibasic anhydride into the solution to prepare a polyamide acid solution containing boron nitride;
5) adding the core-shell heat-conducting filler prepared in the step 3) into the polyamide acid solution containing boron nitride prepared in the step 4), uniformly stirring, and performing vacuum defoaming treatment;
6) and (3) paving a film by using the defoamed polyamic acid solution, performing thermal imidization treatment on the paved film, and cooling after complete thermal imidization to obtain the high-thermal-conductivity polyimide film.
In the step 3), the concentration of the boron nitride dispersion liquid is 1-10mg/ml, and the mass ratio of the modified boron nitride to the modified alumina is 1: 1-10.
Has the advantages that: the invention provides a high-thermal-conductivity polyimide film prepared from core-shell structure thermal-conductivity filler and a preparation method thereof, wherein the preparation principle of the film is as follows: spherical alumina is modified by a silane coupling agent KH550 to enable the surface of the spherical alumina to have positive charges, boron nitride is oxidized at high temperature to enable the spherical alumina to have negative charges, a core-shell heat-conducting filler of boron nitride nanosheet coated alumina is prepared by an electrostatic self-assembly method, a synergistic heat-conducting network structure is formed by the core-shell heat-conducting filler and the boron nitride, dianhydride and diamine in the matrix phase are subjected to dehydration condensation polyaddition reaction in equimolar amounts, and a two-step method is used for preparing the polyimide composite film with high heat conductivity. The polyimide film with high thermal conductivity has the two advantages that an effective thermal conduction path is formed, and the thermal conduction loss at an interface is reduced; in a polyimide matrix, the core-shell heat-conducting filler and the boron nitride filler can cooperate well to form an isolated three-dimensional heat-conducting network structure, the heat-conducting network structure can enable phonons to be effectively transmitted in the polyimide matrix, the surface of the core-shell heat-conducting filler is coated with boron nitride, the core of the core-shell heat-conducting filler is aluminum oxide, the core-shell heat-conducting filler and the aluminum oxide are both high heat-conducting fillers, the inside of the core-shell heat-conducting filler is an interface of aluminum oxide and boron nitride which are subjected to electrostatic self-assembly, and the interface of boron nitride and boron nitride is arranged outside the core-shell heat-conducting filler, so that interface. Compared with the existing polyimide heat-conducting film in the market, the single heat-conducting filler is added by adopting a blending method, an effective heat-conducting path is not formed, and a mode for reducing heat-conducting loss at an interface is not provided; the film of the present invention has greatly lowered production cost, including boron nitride in the price of 1000-4000 yuan per kg and alumina in the price of 100 yuan per kg, and the present invention has alumina to replace partial boron nitride stuffing and core-shell heat conducting stuffing in the cost of 500 yuan per kg, so that the cost of preparing core-shell heat conducting stuffing is lowered by 50-70% compared with that of adding only boron nitride stuffing. In conclusion, the invention provides a high-thermal-conductivity polyimide film prepared from the core-shell structure thermal-conductivity filler and a preparation method thereof.
Drawings
FIG. 1 is a scanning electron microscope image of a prepared boron nitride-coated alumina heat-conductive filler;
FIG. 1 shows that boron nitride coated alumina is prepared by an electrostatic self-assembly method and forms an isolated heat conducting network with boron nitride inside a polyimide matrix.
Detailed Description
The invention is further described below by way of examples, but is not limited thereto.
The preparation method of the core-shell heat-conducting filler comprises the following steps:
(1) preparation of KH550 modified alumina: using absolute ethyl alcohol and deionized water according to the proportion of 1: 5, dropwise adding glacial acetic acid to adjust the pH of the dispersion to 5, slowly dropwise adding 4.3g of KH550 into the dispersion, mechanically stirring for 2h to hydrolyze the KH550, then adding 20g of alumina, heating in a water bath at 60 ℃ for 2h, reacting, and centrifugally drying to obtain KH550 modified alumina;
(2) preparing modified boron nitride: weighing 20g of boron nitride, putting the boron nitride into a muffle furnace, setting a program for heating, calcining for 2h in an air atmosphere at 900 ℃, taking deionized water as a dispersion liquid, carrying out ultrasonic treatment on the calcined boron nitride for 2h, and then carrying out centrifugal drying to obtain modified boron nitride;
(3) preparing boron nitride coated alumina: weighing the modified boron nitride prepared in the step (2), adding deionized water, preparing boron nitride dispersion liquid with the concentration of 4mg/ml, carrying out ultrasonic treatment for 1h, dropwise adding glacial acetic acid to adjust the pH value of the boron nitride dispersion liquid to be 4, adding the modified aluminum oxide prepared in the step (1) to obtain KH550, wherein the mass ratio of the modified boron nitride to the modified aluminum oxide is 1: and 5, mechanically stirring for 2 hours, and then centrifugally drying to obtain the boron nitride-coated alumina core-shell heat-conducting filler, wherein a scanning electron microscope image of the boron nitride-coated alumina core-shell heat-conducting filler is shown in fig. 1, as can be seen from the scanning electron microscope image, the lamellar boron nitride is coated on the spherical alumina, and the core-shell heat-conducting filler and the boron nitride can cooperatively form a heat-conducting network structure in a polyimide matrix.
Example 1
A preparation method of a high-thermal-conductivity polyimide film comprises the following steps:
(1) adding 3.15g of boron nitride into 82g of DMAC dispersion liquid for ultrasonic treatment for 2 hours, adding 8.615g of ODA, and mechanically stirring to dissolve the boron nitride to prepare a reaction solvent containing the boron nitride after ultrasonic stripping;
(2) adding 9.385g of PMDA divided into 50%, 20% and 8% into the reaction solvent obtained in the step (1) for four times, wherein each time interval is 0.5h, and the rest 2% of PDMA adjusts the system viscosity to enable the system viscosity to reach 50000 MPa & s, so as to prepare a polyamic acid solution containing boron nitride;
(3) adding 3.15g of boron nitride-coated alumina heat-conducting filler into the prepared boron nitride-containing polyamic acid solution, mechanically stirring for about 3 hours, and placing the mixture into a vacuum oven for defoaming under-1 MPa;
(4) and (2) paving a film by using the defoamed polyamic acid solution, putting the paved film into a high-temperature oven for thermal imidization, setting the heating rate of the oven to be 2 ℃/min, keeping the temperature of the oven for 20min from room temperature after the temperature of the oven rises to 40 ℃ until the temperature reaches 350 ℃, and cooling to obtain the high-thermal-conductivity polyimide film after complete thermal imidization.
The prepared polyimide film is subjected to heat conductivity test by a laser flash method, and the in-plane heat conductivity coefficient of the film is 4.13W (m.K)-1The out-of-plane thermal conductivity coefficient is 0.55W (m.K)-1。
Example 2
A preparation method of a high-thermal-conductivity polyimide film comprises the following steps:
(1) adding 4.2g of boron nitride into 82g of DMAC dispersion liquid for ultrasonic treatment for 2 hours, adding 8.615g of ODA, and mechanically stirring to dissolve the boron nitride to prepare a reaction solvent containing the boron nitride after ultrasonic stripping;
(2) adding 9.385g of PMDA divided into 50%, 20% and 8% into the reaction solvent obtained in the step (1) for four times, wherein each time interval is 0.5h, and the rest 2% of PDMA adjusts the system viscosity to enable the system viscosity to reach 50000 MPa & s, so as to prepare a polyamic acid solution containing boron nitride;
(3) adding 2.1g of boron nitride-coated alumina heat-conducting filler into the prepared boron nitride-containing polyamic acid solution, mechanically stirring for about 3 hours, and placing the mixture into a vacuum oven for defoaming under-1 MPa;
(4) and (2) paving a film by using the defoamed polyamic acid solution, putting the paved film into a high-temperature oven for thermal imidization, setting the heating rate of the oven to be 2 ℃/min, keeping the temperature of the oven for 20min from room temperature after the temperature of the oven rises to 40 ℃ until the temperature reaches 350 ℃, and cooling to obtain the high-thermal-conductivity polyimide film after complete thermal imidization.
Will be prepared intoThe polyimide film of (1) was subjected to a thermal conductivity test by a laser flash method, and the film had an in-plane thermal conductivity of 3.92W (m.K)-1The out-of-plane thermal conductivity coefficient is 0.53W (m.K)-1。
Example 3
A preparation method of a high-thermal-conductivity polyimide film comprises the following steps:
(1) 4.725g of boron nitride is added into 82g of DMAC dispersion liquid for ultrasonic treatment for 2 hours, then 8.615g of ODA is added, and the boron nitride is dissolved by mechanical stirring to prepare a reaction solvent containing the boron nitride after ultrasonic stripping;
(2) adding 9.385g of PMDA divided into 50%, 20% and 8% into the reaction solvent obtained in the step (1) for four times, wherein each time interval is 0.5h, and the rest 2% of PDMA adjusts the system viscosity to enable the system viscosity to reach 50000 MPa & s, so as to prepare a polyamic acid solution containing boron nitride;
(3) adding 1.575g of boron nitride-coated alumina heat-conducting filler into the prepared boron nitride-containing polyamic acid solution, mechanically stirring for about 3 hours, and placing the mixture into a vacuum oven for defoaming under-1 MPa;
(4) and (2) paving a film by using the defoamed polyamic acid solution, putting the paved film into a high-temperature oven for thermal imidization, setting the heating rate of the oven to be 2 ℃/min, keeping the temperature of the oven for 20min from room temperature after the temperature of the oven rises to 40 ℃ until the temperature reaches 350 ℃, and cooling to obtain the high-thermal-conductivity polyimide film after complete thermal imidization.
The prepared polyimide film is subjected to heat conductivity test by a laser flash method, and the in-plane heat conductivity coefficient of the film is 4.02W (m.K)-1The out-of-plane thermal conductivity coefficient is 0.47W (m.K)-1。
Example 4
A preparation method of a high-thermal-conductivity polyimide film comprises the following steps:
(1) adding 1.26g of boron nitride into 82g of DMAC dispersion liquid for ultrasonic treatment for 2 hours, adding 8.615g of ODA, and mechanically stirring to dissolve the boron nitride to prepare a reaction solvent containing the boron nitride after ultrasonic stripping;
(2) adding 9.385g of PMDA divided into 50%, 20% and 8% into the reaction solvent obtained in the step (1) for four times, wherein each time interval is 0.5h, and the rest 2% of PDMA adjusts the system viscosity to enable the system viscosity to reach 50000 MPa & s, so as to prepare a polyamic acid solution containing boron nitride;
(3) adding 5.04g of heat-conducting filler of boron nitride-coated alumina into the prepared polyamide acid solution containing boron nitride, mechanically stirring for about 3 hours, and placing the mixture into a vacuum oven for defoaming under-1 MPa;
(4) and (2) paving a film by using the defoamed polyamic acid solution, putting the paved film into a high-temperature oven for thermal imidization, setting the heating rate of the oven to be 2 ℃/min, keeping the temperature of the oven for 20min from room temperature after the temperature of the oven rises to 40 ℃ until the temperature reaches 350 ℃, and cooling to obtain the high-thermal-conductivity polyimide film after complete thermal imidization.
The prepared polyimide film is subjected to heat conductivity test by a laser flash method, and the in-plane heat conductivity coefficient of the film is 4.32W (m.K)-1The out-of-plane thermal conductivity coefficient is 0.61W (m.K)-1。
Example 5
A preparation method of a high-thermal-conductivity polyimide film comprises the following steps:
(1) adding 1.08g of boron nitride into 82g of DMAC dispersion liquid for ultrasonic treatment for 2 hours, adding 8.615g of ODA, and mechanically stirring to dissolve the boron nitride to prepare a reaction solvent containing the boron nitride after ultrasonic stripping;
(2) adding 9.385g of PMDA divided into 50%, 20% and 8% into the reaction solvent obtained in the step (1) for four times, wherein each time interval is 0.5h, and the rest 2% of PDMA adjusts the system viscosity to enable the system viscosity to reach 50000 MPa & s, so as to prepare a polyamic acid solution containing boron nitride;
(3) adding 4.32g of boron nitride-coated alumina heat-conducting filler into the prepared boron nitride-containing polyamic acid solution, mechanically stirring for about 3 hours, and placing the mixture into a vacuum oven for defoaming under-1 MPa;
(4) and (2) paving a film by using the defoamed polyamic acid solution, putting the paved film into a high-temperature oven for thermal imidization, setting the heating rate of the oven to be 2 ℃/min, keeping the temperature of the oven for 20min from room temperature after the temperature of the oven rises to 40 ℃ until the temperature reaches 350 ℃, and cooling to obtain the high-thermal-conductivity polyimide film after complete thermal imidization.
The prepared polyimide film is subjected to heat conductivity test by a laser flash method, and the in-plane thermal conductivity of the film is 4.62W (m.K)-1The out-of-plane thermal conductivity coefficient is 0.69W (m.K)-1。
The thermal conductivity of the polyimide film prepared in examples 1 to 5 was compared with that of the polyimide film prepared in the domestic and foreign fields by a laser flash method, and the polyimide film prepared in the present invention has a high thermal conductivity. Due to the price ratio of the h-BN raw material on the market to Al2O3The price of the raw materials is much higher, so the composite film can not only improve certain heat-conducting performance, but also reduce the cost and increase the profit in the processing technology. The film of the invention has better application field and larger market space at present.
Claims (6)
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| CN112063020B (en) * | 2020-09-04 | 2021-09-07 | 四川大学 | A core-shell spherical thermally conductive filler and its preparation method and application |
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Application publication date: 20191115 Assignee: Guangxi Baoci New Materials Co.,Ltd. Assignor: GUILIN University OF ELECTRONIC TECHNOLOGY Contract record no.: X2022450000276 Denomination of invention: High thermal conductivity polyimide film prepared by core-shell thermal conductive filler and its preparation method Granted publication date: 20210302 License type: Common License Record date: 20221209 |
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