CN112708274A - Heat-conducting insulating polyimide film and preparation method thereof - Google Patents
Heat-conducting insulating polyimide film and preparation method thereof Download PDFInfo
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- CN112708274A CN112708274A CN202011588843.XA CN202011588843A CN112708274A CN 112708274 A CN112708274 A CN 112708274A CN 202011588843 A CN202011588843 A CN 202011588843A CN 112708274 A CN112708274 A CN 112708274A
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- polyethylene glycol
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- 229920001721 polyimide Polymers 0.000 title claims abstract description 51
- 238000002360 preparation method Methods 0.000 title claims description 7
- 150000004985 diamines Chemical class 0.000 claims abstract description 54
- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 claims abstract description 47
- 239000000945 filler Substances 0.000 claims abstract description 41
- 239000002202 Polyethylene glycol Substances 0.000 claims abstract description 32
- 229920001223 polyethylene glycol Polymers 0.000 claims abstract description 32
- 239000007788 liquid Substances 0.000 claims abstract description 29
- 229920005575 poly(amic acid) Polymers 0.000 claims abstract description 29
- 239000006185 dispersion Substances 0.000 claims abstract description 28
- 239000002904 solvent Substances 0.000 claims abstract description 19
- 239000004642 Polyimide Substances 0.000 claims abstract description 16
- 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 abstract description 16
- 239000002798 polar solvent Substances 0.000 claims abstract description 14
- 238000006243 chemical reaction Methods 0.000 claims abstract description 7
- 239000003607 modifier Substances 0.000 claims abstract description 7
- 238000002156 mixing Methods 0.000 claims abstract description 6
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims abstract description 4
- 229910052796 boron Inorganic materials 0.000 claims abstract description 4
- 239000002131 composite material Substances 0.000 claims abstract description 4
- 238000012986 modification Methods 0.000 claims abstract description 4
- 230000004048 modification Effects 0.000 claims abstract description 4
- 229910052582 BN Inorganic materials 0.000 claims description 20
- 238000000034 method Methods 0.000 claims description 14
- 238000003756 stirring Methods 0.000 claims description 13
- 239000005341 toughened glass Substances 0.000 claims description 13
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical group CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 12
- 239000004576 sand Substances 0.000 claims description 8
- 239000011248 coating agent Substances 0.000 claims description 7
- 238000000576 coating method Methods 0.000 claims description 7
- 239000007888 film coating Substances 0.000 claims description 7
- 238000009501 film coating Methods 0.000 claims description 7
- 239000000463 material Substances 0.000 claims description 7
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical group CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 6
- 238000011065 in-situ storage Methods 0.000 claims description 6
- 238000006116 polymerization reaction Methods 0.000 claims description 6
- HLBLWEWZXPIGSM-UHFFFAOYSA-N 4-Aminophenyl ether Chemical compound C1=CC(N)=CC=C1OC1=CC=C(N)C=C1 HLBLWEWZXPIGSM-UHFFFAOYSA-N 0.000 claims description 5
- CBCKQZAAMUWICA-UHFFFAOYSA-N 1,4-phenylenediamine Chemical compound NC1=CC=C(N)C=C1 CBCKQZAAMUWICA-UHFFFAOYSA-N 0.000 claims description 3
- 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 claims description 3
- 229910001220 stainless steel Inorganic materials 0.000 claims description 3
- 239000010935 stainless steel Substances 0.000 claims description 3
- 125000006160 pyromellitic dianhydride group Chemical group 0.000 claims 1
- 238000011282 treatment Methods 0.000 claims 1
- 238000009413 insulation Methods 0.000 abstract description 9
- 239000002071 nanotube Substances 0.000 description 16
- 239000010408 film Substances 0.000 description 15
- 239000000203 mixture Substances 0.000 description 6
- VLDPXPPHXDGHEW-UHFFFAOYSA-N 1-chloro-2-dichlorophosphoryloxybenzene Chemical compound ClC1=CC=CC=C1OP(Cl)(Cl)=O VLDPXPPHXDGHEW-UHFFFAOYSA-N 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 4
- 238000004321 preservation Methods 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- 229920000604 Polyethylene Glycol 200 Polymers 0.000 description 3
- 230000009194 climbing Effects 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 229910002804 graphite Inorganic materials 0.000 description 3
- 239000010439 graphite Substances 0.000 description 3
- 230000017525 heat dissipation Effects 0.000 description 3
- 238000005303 weighing Methods 0.000 description 3
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 238000004377 microelectronic Methods 0.000 description 2
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 239000004278 EU approved seasoning Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000010292 electrical insulation Methods 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 235000011194 food seasoning agent Nutrition 0.000 description 1
- 239000012212 insulator Substances 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- 238000013021 overheating Methods 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/1067—Wholly aromatic polyimides, i.e. having both tetracarboxylic and diamino moieties aromatically bound
- C08G73/1071—Wholly aromatic polyimides containing oxygen in the form of ether bonds in the main chain
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K5/00—Heat-transfer, heat-exchange or heat-storage materials, e.g. refrigerants; Materials for the production of heat or cold by chemical reactions other than by combustion
- C09K5/08—Materials not undergoing a change of physical state when used
- C09K5/14—Solid materials, e.g. powdery or granular
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- 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
-
- C—CHEMISTRY; METALLURGY
- 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
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
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- C—CHEMISTRY; METALLURGY
- 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
- C08K7/00—Use of ingredients characterised by shape
- C08K7/22—Expanded, porous or hollow particles
- C08K7/24—Expanded, porous or hollow particles inorganic
-
- C—CHEMISTRY; METALLURGY
- 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
- C08K9/00—Use of pretreated ingredients
- C08K9/04—Ingredients treated with organic substances
Abstract
The invention relates to a heat-conducting insulating polyimide film, which comprises a modifier polyethylene glycol diamine, a multi-wall nano boron nitride tube, an organic polar solvent, a solvent, diamine and dianhydride; the dosage of the modifier, namely the polyethylene glycol diamine is 5 to 10 percent of the mass of boron in the multi-wall nano boron nitride tube; adding a multi-walled nano boron nitride tube and polyethylene glycol diamine into an organic polar solvent to obtain an inorganic heat-conducting filler dispersion liquid with the surface modified by the polyethylene glycol diamine; mixing the obtained inorganic heat-conducting filler dispersion liquid after the surface modification of the polyethylene glycol diamine with a solvent, diamine and dianhydride for reaction to prepare polyamic acid with required filler; the multi-wall nano boron nitride tube has the diameter of 30-120 nm, the length of 0.8-7 mu m and the addition amount of 10-30% of the total mass of the polyimide composite film. The produced polyimide film has high heat conductivity coefficient and is non-conductive, and can be applied to a plurality of fields such as a heat insulation pad (radiator), a heater circuit and the like.
Description
Technical Field
The invention relates to the field of film manufacturing, in particular to a heat-conducting insulating polyimide film and a preparation method thereof.
Background
With the rapid development of the electronic information industry, the high integration, high density and high speed of electronic equipment enable a circuit or a chip to quickly accumulate heat in a tiny limited space, the electronic chip has extremely strict requirements on heat dissipation, if the heat generated in the operation of the electronic equipment cannot be released in time, thermal failure can be caused, according to statistics, the failure modes of the electronic equipment exceeding 55% are caused by overhigh temperature, and when the internal temperature exceeds the limit temperature of the electronic element, the element can be burnt, even a fire disaster occurs. Therefore, heat dissipation and heat protection design is a new need for electronic equipment, and with the development of 5G mobile phones/base stations, data centers, automotive electronics and AIoT, the heat dissipation needs are rapidly increased.
Polyimide (PI) has excellent thermal stability, electrical insulation, mechanical property and lower dielectric property, and is widely applied to the fields of microelectronics, rail transit, aerospace and the like. However, the heat conductivity coefficient of the conventional PI film is only about 0.16W/(m · K), and almost a thermal insulator, so that when the PI film is applied to high-density and high-speed operation of microelectronics, circuit overheating easily occurs, and the stability of components and integrated circuits is affected.
At present, most of polyimide heat-conducting films in China use aluminum oxide, graphite and h-BN as heat-conducting media to improve the heat-conducting property of a matrix, and the heat-conducting property is improved to some extent, but the polyimide heat-conducting films have advantages and disadvantages. Alumina is low in price and is the preferred heat-conducting filler, but because the heat conductivity coefficient of alumina is low and is only 35W/(m.K), the heat-conducting property can be improved only by the large amount of filling amount, and the mechanical property of the material is inevitably reduced. Graphite as a representative heat conducting material has high heat conducting capacity, but is difficult to disperse and expensive, and has electric conductivity, and graphite is not usually selected when heat conducting seasonings are selected. Although h-BN is the most commonly used heat-conducting filler at present, the heat-conducting property is good, but the dispersion capability is poor due to the regular in-plane orientation, the h-BN is generally dispersed into single-layer h-BN by a chemical and physical dispersion method, the working procedure is more duplicated, and the application range of the h-BN is limited.
Disclosure of Invention
The invention provides an insulating and heat-conducting polyimide film and a manufacturing method thereof, and the produced polyimide film has high heat conductivity coefficient and is non-conducting and can be applied to multiple fields of heat insulation pads (radiators), heater circuits and the like.
The invention realizes the aim through the following technical scheme: a heat-conducting insulating polyimide film comprises a modifier polyethylene glycol diamine, a multi-walled nano boron nitride tube, an organic polar solvent, a solvent, diamine and dianhydride; the dosage of the modifier, namely the polyethylene glycol diamine is 5 to 10 percent of the mass of boron in the multi-wall nano boron nitride tube; adding a multi-walled nano boron nitride tube and polyethylene glycol diamine into an organic polar solvent to obtain an inorganic heat-conducting filler dispersion liquid with the surface modified by the polyethylene glycol diamine; mixing the obtained inorganic heat-conducting filler dispersion liquid after the surface modification of the polyethylene glycol diamine with a solvent, diamine and dianhydride for reaction to prepare polyamic acid with required filler;
the multi-wall nano boron nitride tube has the diameter of 30-120 nm, the length of 0.8-7 mu m and the addition amount of 10-30% of the total mass of the polyimide composite film.
Furthermore, the tensile strength of the multi-wall nano boron nitride tube is more than 50GPa, and the thermal conductivity is more than 2500W/(m.K).
Further, the organic polar solvent is an N, N-dimethylformamide solvent.
Further, the solvent is dimethylacetamide.
Further, the diamine is diamine (4, 4)，-diaminodiphenyl ether) or p-phenylenediamine, said dianhydride being pyromellitic dianhydride or biphenyltetracarboxylic dianhydride.
Furthermore, the flat plate is a toughened glass plate or a stainless steel plate, and the thickness of the thin film coated on the flat plate is 5-200 microns.
Still further, the thickness of the film applied to the flat sheet was 50 μm.
A preparation method of a heat-conducting insulating polyimide film comprises the following steps:
step 1): adding a multi-walled nano boron nitride tube and polyethylene glycol diamine into an organic polar solvent, and uniformly stirring and dispersing by a sand mill to obtain an inorganic heat-conducting filler dispersion liquid with the surface modified by the polyethylene glycol diamine;
step 2): mixing and reacting the modified inorganic heat-conducting filler dispersion liquid filler with a solvent, diamine and dianhydride by adopting an in-situ polymerization method to prepare polyamic acid with required filler;
step 3): then, uniformly coating polyamic acid on a plane plate by using a film coating machine, and then putting the plane plate into a high-temperature oven for imidization to generate the required polyimide;
step 4): and finally, taking out the product to peel off the polyimide film on the plane plate to obtain the required material.
Further, the imidization temperature of the polyamic acid generated in the step 3) in the high-temperature oven is 60 ℃ and 45min, and then the heat preservation is performed sequentially for 10min at the temperature of 110 ℃, 5min at the temperature of 200 ℃, 5min at the temperature of 250 ℃ and 3min at the temperature of 350 ℃.
The invention has the beneficial effects that: the produced polyimide film has high heat conductivity coefficient and is non-conductive, and can be applied to a plurality of fields such as a heat insulation pad (radiator), a heater circuit and the like.
Drawings
FIG. 1 is a schematic diagram of a multi-walled nano boron nitride tube useful in the present invention;
FIG. 2 is a schematic flow diagram of a production process of the present invention;
FIG. 3 is a schematic diagram of the modified front and back structures of a multi-walled boron nitride nanotube according to the present invention.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The invention discloses an insulating heat-conducting polyimide film and a manufacturing method thereof. Adding a multi-walled nano boron nitride tube and polyethylene glycol diamine into an organic polar solvent, and uniformly stirring and dispersing by a sand mill to obtain an inorganic heat-conducting filler dispersion liquid with the surface modified by the polyethylene glycol diamine; the method adopts an in-situ polymerization method to mix and react pre-dispersed fillers (namely the obtained inorganic heat-conducting filler dispersion liquid after the surface of polyethylene glycol diamine is modified) with a solvent, diamine and dianhydride to prepare the polyamic acid with the required fillers. Then, a film coating machine is used for uniformly coating the polyamic acid on a plane plate, and the plane plate is put into a high-temperature oven for imidization to generate the required polyimide (soft film). And finally, taking out the product to peel off the polyimide film on the plane plate to obtain the required material. The polyimide film prepared by the method has the characteristics of insulation and good heat conduction, and can be applied to multiple fields of heat insulation pads (radiators), heater circuits and the like.
Furthermore, the multi-wall nanometer boron nitride pipe adopts a Nanointegris multi-wall nanometer boron nitride pipe.
The organic polar solvent is N, N-dimethylformamide solvent.
The solvent is dimethylacetamide.
The diamine may be diamine (4, 4)，Diaminodiphenyl ether), p-phenylenediamine, etc., and the dianhydride may be pyromellitic dianhydride or biphenyltetracarboxylic dianhydride.
The flat plate can be a toughened glass plate or a stainless steel plate, and the thickness of the film coated on the flat plate is 5-200 microns.
The in-situ (polymerization method) reaction means that the surface of the modified boron nitride nanotube has amino, and the amino can participate in the synthesis reaction, so that the dispersion uniformity of the heat-conducting filler is improved, and the construction of a heat-conducting network is facilitated.
The heat-conducting insulating polyimide film and the preparation method thereof are specifically explained below, and the multi-wall nano boron nitride tube, the multi-wall boron nitride nanotube and the multi-wall boron nitride tube are all multi-wall nano boron nitride tube structures.
An insulating heat-conducting polyimide film is characterized in that polyethylene glycol diamine is used for modifying a multi-walled nano boron nitride tube, the amount of the modifier polyethylene glycol diamine is 5% -10% of the mass of boron of the multi-walled nano boron nitride tube, the multi-walled nano boron nitride tube and the polyethylene glycol diamine are added into an organic polar solvent and stirred and dispersed uniformly by a sand mill, and inorganic heat-conducting filler dispersion liquid after the surface of the polyethylene glycol diamine is modified is obtained; the diameter of the multi-wall boron nitride nanotube is 30-120 nm, the length of the multi-wall boron nitride nanotube is 0.8-7 mu m, the addition amount of the multi-wall boron nitride nanotube is 10-30% of the total mass of the polyimide composite film, the tensile strength of the multi-wall boron nitride nanotube is more than 50GPa, and the thermal conductivity of the multi-wall boron nitride nanotube is more than 2500W/(m.K).
Further, the temperature for imidization in the high-temperature oven is 60 ℃ and 45min, then 110 ℃ and 10min,200 ℃ and 5min, 270 ℃ and 350 ℃ are sequentially kept for 3 min.
Specifically, the preparation method of the insulating heat-conducting polyimide film comprises the following steps
Step 1): adding a multi-walled nano boron nitride tube and polyethylene glycol diamine into an organic polar solvent, and uniformly stirring and dispersing by a sand mill to obtain an inorganic heat-conducting filler dispersion liquid with the surface modified by the polyethylene glycol diamine;
step 2): adopting an in-situ polymerization method to mix and react modified (inorganic heat-conducting filler dispersion) filler with solvent, diamine and dianhydride to prepare polyamic acid with required filler;
step 3): then, uniformly coating polyamic acid on a plane plate by using a film coating machine, and then putting the plane plate into a high-temperature oven for imidization to generate the required polyimide (soft film);
step 4): finally, the product is taken out, and the polyimide film (hard mold) on the plane plate is peeled off, so that the required material can be prepared.
The filler adopted in the method is the multi-wall nano boron nitride tube, the multi-wall boron nitride tube has low friction coefficient, high temperature resistance and good heat conductivity coefficient, and can effectively improve the heat conductivity of the polyimide.
The planar sheet material used may be a tempered glass sheet, preferably, the thickness of the film applied to the planar sheet material is 50 μm.
The imidization temperature of the generated polyamic acid in a high-temperature oven is 60 ℃ and 45min, then the temperature is sequentially kept for 10min at 110 ℃, 5min at 200 ℃, 5min at 250 ℃ and 3min at 350 ℃.
The invention has the beneficial effects that:
1: according to the invention, the multi-wall nano boron nitride tube is selected as the heat-conducting filler, and has a very large length-diameter ratio, so that the heat exchange performance along the length direction is very high, only a small amount of multi-wall boron nitride nanotubes are doped in the polyimide matrix, the heat conductivity is greatly improved on the premise of insulation, and the influence on the mechanical property is small.
2: the polyethylene glycol diamine is used for modifying the multi-wall boron nitride nanotube, and the dispersion uniformity of the multi-wall boron nitride nanotube heat-conducting filler is improved by adopting an in-situ polymerization synthesis mode.
Example 1:
(1) 20g of 100nm multi-wall boron nitride nanotube inorganic heat-conducting filler and 1.5g of polyethylene glycol diamine (NH)2-PEG(200)-NH 2) Adding the mixture into a 300g N N-dimethylformamide solvent, and uniformly stirring and dispersing the mixture at a high speed by a sand mill to obtain an inorganic heat-conducting filler dispersion liquid after the surface of the polyethanediol diamine is modified;
(2) adding the modified multi-walled boron nitride nanotube dispersion (i.e., the inorganic heat-conducting filler dispersion described in this embodiment) into a reaction kettle containing 400g of dimethylacetamide, sequentially weighing 50g of diaminodiphenyl ether, slowly adding 63.2g of pyromellitic dianhydride while stirring, and stirring until the viscosity of the solution increases and the rod climbing phenomenon occurs. And taking out the liquid (polyamic acid), uniformly coating the liquid (polyamic acid) on a toughened glass plate by using an automatic film coating machine to enable the film thickness of the liquid (polyamic acid) to be 50 microns, then putting the toughened glass plate coated with the polyamic acid solution into a high-temperature oven, controlling the temperature rise and preservation speed to imidize the liquid (polyamic acid), wherein the imidization process comprises the steps of preserving heat at 60 ℃ for 45min, preserving heat at 110 ℃ for 10min, preserving heat at 200 ℃ for 5min, preserving heat at 270 ℃ for 5min and preserving heat at 350 ℃ for 3 min. And finally, when the temperature of the oven is reduced, taking out the plate toughened glass plate, and peeling off the polyimide film to obtain the polyimide film with insulation and heat conduction.
Example 2:
(1) mixing 11.3g of 100nm multi-wall boron nitride nanotube inorganic heat-conducting filler and 1.0g of polyethylene glycol diamine (NH)2-PEG(200)-NH 2) Adding the mixture into a 150g N N-dimethylformamide solvent, and uniformly stirring and dispersing the mixture at a high speed by a sand mill to obtain an inorganic heat-conducting filler dispersion liquid after the surface of the polyethanediol diamine is modified;
(2) adding the modified multi-walled boron nitride nanotube dispersion (i.e., the inorganic heat-conducting filler dispersion described in this embodiment) into a reaction kettle containing 400g of dimethylacetamide, sequentially weighing 50g of diaminodiphenyl ether, slowly adding 63.2g of pyromellitic dianhydride while stirring, and stirring until the viscosity of the solution increases and the rod climbing phenomenon occurs. And taking out the liquid (polyamic acid), uniformly coating the liquid (polyamic acid) on a toughened glass plate by using an automatic film coating machine to enable the film thickness of the liquid (polyamic acid) to be 50 microns, then putting the toughened glass plate coated with the polyamic acid solution into a high-temperature oven, controlling the temperature rise and preservation speed to imidize the liquid (polyamic acid), wherein the imidization process comprises the steps of preserving heat at 60 ℃ for 45min, preserving heat at 110 ℃ for 10min, preserving heat at 200 ℃ for 5min, preserving heat at 270 ℃ for 5min and preserving heat at 350 ℃ for 3 min. And finally, when the temperature of the oven is reduced, taking out the plate toughened glass plate, and peeling off the polyimide film to obtain the polyimide film with insulation and heat conduction.
Example 3:
(1) 34g of 100nm multi-wall boron nitride nanotube inorganic heat-conducting filler and 2.5g of polyethylene glycol diamine (NH)2-PEG(200)-NH 2) Adding the mixture into 400g N, and uniformly stirring and dispersing the mixture in an N-dimethylformamide solvent at a high speed by a sand mill to obtain an inorganic heat-conducting filler dispersion liquid after the surface of the polyethanediol diamine is modified;
(2) adding the modified multi-walled boron nitride nanotube dispersion (i.e., the inorganic heat-conducting filler dispersion described in this embodiment) into a reaction kettle containing 400g of dimethylacetamide, sequentially weighing 50g of diaminodiphenyl ether, slowly adding 63.2g of pyromellitic dianhydride while stirring, and stirring until the viscosity of the solution increases and the rod climbing phenomenon occurs. And taking out the liquid (polyamic acid), uniformly coating the liquid (polyamic acid) on a toughened glass plate by using an automatic film coating machine to enable the film thickness of the liquid (polyamic acid) to be 50 microns, then putting the toughened glass plate coated with the polyamic acid solution into a high-temperature oven, controlling the temperature rise and preservation speed to imidize the liquid (polyamic acid), wherein the imidization process comprises the steps of preserving heat at 60 ℃ for 45min, preserving heat at 110 ℃ for 10min, preserving heat at 200 ℃ for 5min, preserving heat at 270 ℃ for 5min and preserving heat at 350 ℃ for 3 min. And finally, when the temperature of the oven is reduced, taking out the plate toughened glass plate, and peeling off the polyimide film to obtain the polyimide film with insulation and heat conduction.
The following are the thermal conductivity data for each polyimide film in the above examples:
| serial number | Thermal conductivity (W/(m.K)) |
| Example 1 | 0.47 |
| Example 2 | 0.88 |
| Example 3 | 1.52 |
To be provided with
The present invention is not limited to the above-described preferred embodiments, but rather, the present invention is to be construed broadly and cover all modifications, equivalents, and improvements falling within the spirit and scope of the present invention.
Claims (9)
1. A heat-conducting insulating polyimide film is characterized by comprising a modifier polyethylene glycol diamine, a multi-wall nanometer boron nitride tube, an organic polar solvent, a solvent, diamine and dianhydride; the dosage of the modifier, namely the polyethylene glycol diamine is 5 to 10 percent of the mass of boron in the multi-wall nano boron nitride tube; adding a multi-walled nano boron nitride tube and polyethylene glycol diamine into an organic polar solvent to obtain an inorganic heat-conducting filler dispersion liquid with the surface modified by the polyethylene glycol diamine; mixing the obtained inorganic heat-conducting filler dispersion liquid after the surface modification of the polyethylene glycol diamine with a solvent, diamine and dianhydride for reaction to prepare polyamic acid with required filler;
the multi-wall nano boron nitride tube has the diameter of 30-120 nm, the length of 0.8-7 mu m and the addition amount of 10-30% of the total mass of the polyimide composite film.
2. The thermally conductive and insulating polyimide film according to claim 1, wherein: the tensile strength of the multi-wall nano boron nitride tube is more than 50GPa, and the thermal conductivity is more than 2500W/(m.K).
3. The thermally conductive and insulating polyimide film according to claim 1, wherein: the organic polar solvent is N, N-dimethylformamide solvent.
4. The thermally conductive and insulating polyimide film according to claim 1, wherein: the solvent is dimethylacetamide.
5. The thermally conductive and insulating polyimide film according to claim 1, wherein: the diamine is diamine (4, 4' -diaminodiphenyl ether) or p-phenylenediamine, and the dianhydride is pyromellitic dianhydride or biphenyl tetracarboxylic dianhydride.
6. The thermally conductive and insulating polyimide film according to claim 1, wherein: the flat plate is a toughened glass plate or a stainless steel plate, and the thickness of the film coated on the flat plate is 5-200 microns.
7. The thermally conductive and insulating polyimide film according to claim 6, wherein: the film thickness was 50 μm when applied to a flat sheet.
8. A preparation method of a heat-conducting insulating polyimide film is characterized by comprising the following steps:
step 1): adding a multi-walled nano boron nitride tube and polyethylene glycol diamine into an organic polar solvent, and uniformly stirring and dispersing by a sand mill to obtain an inorganic heat-conducting filler dispersion liquid with the surface modified by the polyethylene glycol diamine;
step 2): mixing and reacting the modified inorganic heat-conducting filler dispersion liquid filler with a solvent, diamine and dianhydride by adopting an in-situ polymerization method to prepare polyamic acid with required filler;
step 3): then, uniformly coating polyamic acid on a plane plate by using a film coating machine, and then putting the plane plate into a high-temperature oven for imidization to generate the required polyimide;
step 4): and finally, taking out the product to peel off the polyimide film on the plane plate to obtain the required material.
9. The method for preparing a heat-conducting insulating polyimide film as claimed in claim 8, wherein the imidization temperature of the polyamic acid generated in step 3) in the high-temperature oven is 60 ℃ and 45min, and then the treatments of 110 ℃ and 10min,200 ℃ and 5min, 250 ℃ and 350 ℃ are sequentially performed for 3 min.
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