CN110452418A - A kind of high thermal conductivity Kapton and preparation method thereof of core-shell structure heat filling preparation - Google Patents
A kind of high thermal conductivity Kapton and preparation method thereof of core-shell structure heat filling preparation Download PDFInfo
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- CN110452418A CN110452418A CN201910912358.4A CN201910912358A CN110452418A CN 110452418 A CN110452418 A CN 110452418A CN 201910912358 A CN201910912358 A CN 201910912358A CN 110452418 A CN110452418 A CN 110452418A
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- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
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- C08J5/18—Manufacture of films or sheets
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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
- 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
- C08K9/00—Use of pretreated ingredients
- C08K9/04—Ingredients treated with organic substances
- C08K9/06—Ingredients treated with organic substances with silicon-containing compounds
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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
- 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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- 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
- C08K2003/382—Boron-containing compounds and nitrogen
- C08K2003/385—Binary compounds of nitrogen with boron
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- C08K2201/00—Specific properties of additives
- C08K2201/002—Physical properties
- C08K2201/003—Additives being defined by their diameter
Abstract
The invention discloses a kind of high thermal conductivity Kapton and preparation method thereof of core-shell structure heat filling preparation, heat filling is the heat filling of core-shell structure；Film includes the heat filling of 10-50 mass parts, and the modifying agent of 1-5 mass parts, the polyamic acid solution of 80-500 mass parts, heat filling is the nucleocapsid heat filling of boron nitride coated aluminum oxide；Nucleocapsid heat filling is by modifier treatment aluminium oxide and high-temperature calcination boron nitride, it is prepared using electrostatic self-assembled method, nucleocapsid heat filling is added in polyamic acid solution and is uniformly mixed, after vacuum stands defoaming, it is laid to film, high thermal conductivity Kapton is made in temperature programming hot imidization.The film has the key property of high thermal conductivity coefficient and electrical isolation, and processing cost is lower, and preparation process is simple, and short molding cycle, all has wide practical use in electronics, aerospace, machinery field.
Description
Technical field
The invention belongs to Kapton technical fields, and in particular to a kind of height of core-shell structure heat filling preparation is led
Hot polymerization imide membrane and preparation method thereof.
Background technique
With science and technology fast development, especially in electronic field, the science and technology of emergence be it is with rapid changepl. never-ending changes and improvements, electronic component towards
It minimizes integrated direction to develop, this increases the density of electronic component, and caused heat dissipation problem is also got worse, and influences
Efficiency, safety and the service life of electronic equipment.Kapton is a kind of with good hot property and mechanical performance
High molecular material, especially it have low dielectric constant and loss angle tangent, high thermal stability and storage modulus, answered extensively
For electronic package material.However the intrinsic thermal conductivity of pure Kapton is not led only in the left and right 0.1 W/(m K)
Hot material is unable to satisfy practical application.
A kind of two-dimensional material of boron nitride, hexagonal boron nitride has the layer structure similar to graphite, due to its atom
Grade is flat and the surface of electrical isolation, and relatively low density and cheap price are known as " white graphite alkene ", not only flat
With high thermal conductivity (about 600W/(m K)) and with excellent electrical insulating property on the direction of face.Using boron nitride as thermally conductive
Filler, the heat conduction network that can be built, although the addition of pure boron nitride can be such that the thermal coefficient of Kapton improves,
Obtained polyimides thermally conductive film is modified with boron nitride in 109627472 A of patent CN, but what boron nitride was added
Ratio is excessive, will lead to that cost is very high, and effective passage of heat is not formed in the matrix of polyimides；Same patent CN
Polyimides Heat Conduction Material is made using boron nitride and polyimide microsphere in 106243715 B, but process costs are complicated, need
Polyimide microsphere is made.So in terms of polyimides thermally conductive film, wherein efficient raising thermal coefficient and reduction
Cost in thin-film technique production is two difficulties to be solved.
The thermal coefficient of this Heat Conduction Material promotion at present generally passes through two ways, and one is adding, thermal coefficient is high to be filled out
Material, and innovate the mode and effect of building passage of heat；Another kind is the compatibility by improving matrix and filler, reduces phonon
Interface scattering.When the heat filling for having core-shell structure in matrix is added, matrix and shell matter heat filling act synergistically, can be with
Effective passage of heat is constructed, the three-dimensional dimensional network structure of the formation inside polyimides can be such that phonon quickly transmits；And
And when using aluminium oxide as the heat filling of core, overall cost price is lower.To sum up, pass through nucleocapsid heat filling and heat filling
Collaboration building heat conduction network structure, is dedicated to preparing the Kapton of high thermal conductivity low cost.
Summary of the invention
Aiming at the shortcomings of the prior art, the present invention provides a kind of high thermal conductivity polyamides of core-shell structure heat filling preparation is sub-
Amine film and preparation method thereof.The film has the key property of high thermal conductivity coefficient and electrical isolation, and processing cost is lower, preparation
Simple process, and the characteristics of short molding cycle.
Realize the technical scheme is that
A kind of core-shell structure heat filling, the core-shell structure heat filling are by modifier treatment aluminium oxide and high-temperature calcination
Boron nitride, using boron nitride coated aluminum oxide made from electrostatic self-assembled method.
The aluminium oxide pattern is spherical, partial size 1-30um；Boron nitride is hexagonal boron nitride, partial size 50nm-
5um。
The heat filling, preparation method include the following steps:
(1) it prepares the modified aluminium oxide of KH550: configuring dispersion liquid with dehydrated alcohol and deionized water, wherein the matter of dehydrated alcohol
Amount concentration is 5-60%, and adjusting PH is 5-6, and KH550 is slowly added dropwise into dispersion liquid, and wherein the mass parts of KH550 are dispersion liquid
1-5%；Stirring hydrolysis, adds aluminium oxide, and wherein the mass parts of aluminium oxide are the 10-60% of dispersion liquid, is centrifuged after heating water bath
It is dry, the modified aluminium oxide of KH550 is made；
2) the modified boron nitride of preparation: weighing boron nitride, is point with deionized water after calcining 1-2h under 900-1200 DEG C of environment
Dispersion liquid, centrifugal drying after ultrasound, is made modified boron nitride；
3) aluminium oxide of boron nitride cladding is prepared: the ratio that the mass ratio by modified boron nitride and modified aluminium oxide is 1:1-10
Example weighs boron nitride modified made from step (2), and deionized water is added, and the boron nitride that configuration concentration is 1-10mg/ml disperses
Liquid, it is 4-5 that PH is adjusted after ultrasonic, step (1) is added, the aluminium oxide that KH550 is modified is made, stir centrifugal drying, boron nitride is made
The nucleocapsid heat filling of the aluminium oxide of cladding.
A kind of high thermal conductivity Kapton prepared with core-shell structure heat filling, by the raw material of following proportion by weight
It is prepared, the polyamic acid of the heat filling including 10-50 mass parts, the modifying agent of 1-5 mass parts, 80-500 mass parts is molten
Liquid；
The heat filling is core-shell structure heat filling.
The modifying agent is Silane coupling agent KH550.
The polyamic acid solution after being dissolved in organic solvent by diamine, then dibasic anhydride is added into diamine solution
It is made；The mass ratio of the material of dibasic anhydride and diamine is 1:1-1.05, and polyamic acid solution mass concentration is 15-25%.
The dibasic anhydride is pyromellitic acid dianhydride (PMDA), 3,3,, 4,4,Bibenzene tetracarboxylic dianhydride, 2,3,, 3,4,Connection
Pyromellitic dianhydride, 3,3,, 4,4,Benzophenone tetracarboxylic dianhydride, 2,3,, 6,7,One of naphthalenetetracarbacidic acidic dianhydride；
The diamine is p-phenylenediamine, m-phenylene diamine (MPD), benzidine, 4,4,Diaminodiphenyl ether, p dimethylamine, 3,
4,Diaminodiphenyl ether, 4,4,Diaminodiphenyl-methane, 3,3,One kind of dimethoxy benzidine；
The organic solvent is n,N-dimethylacetamide, n,N-Dimethylformamide, N-Methyl pyrrolidone, dimethyl second
One of amide, dimethyl sulfoxide.
The film, with a thickness of 10-500um.
A kind of preparation method for material of the high thermal conductivity Kapton prepared with core-shell structure heat filling, including walk as follows
It is rapid:
1) it prepares the modified aluminium oxide of KH550: configuring dispersion liquid with dehydrated alcohol and deionized water, wherein the quality of dehydrated alcohol
Concentration is 5-60%, and adjusting PH is 5-6, and KH550 is slowly added dropwise into dispersion liquid, and wherein the mass parts of KH550 are the 1- of dispersion liquid
5%；Stirring hydrolysis, adds aluminium oxide, and wherein the mass parts of aluminium oxide are the 10-60% of dispersion liquid, is centrifuged after heating water bath dry
It is dry, the modified aluminium oxide of KH550 is made；
2) the modified boron nitride of preparation: weighing boron nitride, is point with deionized water after calcining 1-2h under 900-1200 DEG C of environment
Dispersion liquid, centrifugal drying after ultrasound, is made modified boron nitride；
3) it prepares the aluminium oxide of boron nitride cladding: weighing boron nitride modified made from step 2, deionized water is added, configure nitrogen
Change boron dispersion liquid, it is 4-5 that PH is adjusted after ultrasound, step 1) is added, the modified aluminium oxide of KH550 is made, stir centrifugal drying, system
Obtain the nucleocapsid heat filling of boron nitride coated aluminum oxide；
4) after boron nitride being uniformly dispersed in organic dispersions, diamine dissolution is added, then dibasic anhydride system is added into solution
, the polyamic acid solution containing boron nitride is made；
5) nucleocapsid heat filling made from step 3) is added in the polyamic acid solution containing boron nitride made from step 4) and is stirred
After mixing uniformly, vacuum defoaming treatment；
6) plastic film mulch is carried out with the polyamic acid solution of defoaming treatment, the film completed will be laid with and carry out hot imidization processing, it is complete
After full hot imidization, cooling obtains high thermal conductivity Kapton.
In step 3), the concentration of boron nitride dispersion is 1-10mg/ml, the matter of modified boron nitride and modified aluminium oxide
Amount is than being 1:1-10.
The utility model has the advantages that a kind of high thermal conductivity Kapton of core-shell structure heat filling preparation provided by the invention and its
Preparation method, the preparation principle of film are as follows: make its surface with positive electricity with Silane coupling agent KH550 modification ball-aluminium oxide
Lotus, high-temperature oxydation boron nitride make it with negative electrical charge, a kind of boron nitride nanosheet cladding are prepared with electrostatic self-assembled method
The nucleocapsid heat filling of aluminium oxide, and the heat conduction network structure cooperateed with is formed with boron nitride, dianhydride and diamines etc. rub in matrix phase
You measure dehydrating condensation sudden reaction, and having prepared with two-step method has high thermal conductivity polyimide composite film.The present invention provides
A kind of high thermal conductivity Kapton two big advantages be form effective thermally conductive pathways and reduce interface thermally conductive damage
It loses；In the matrix of polyimides, nucleocapsid heat filling can be good at cooperateing with boron nitride filler, and the three-dimensional for forming isolation is led
The network structure of heat, the thermally conductive network of network structure can be such that phonon effectively transmits in polyimide matrix, and the nucleocapsid is thermally conductive
Filler surface is coated with boron nitride, and core is aluminium oxide again, and the two is all the filler of high thermal conductivity, and inside is electrostatic self-assembled
Aluminium oxide and boron nitride interface, the interface of outer silicon nitride boron and boron nitride also can be reduced phonon polyimide-based on interface
The scattering of body median surface.Existing polyimides thermally conductive film in the market is compared, single heat filling is added using blending method, and
Effective thermally conductive pathways are not formed, without the mode of reduction interface conductive heat loss yet；Secondly the film of the application is producing
It is substantially reduced in cost, boron nitride price is every kilogram of 1000-4000 member in the market, and the price of aluminium oxide is but 100 yuan every thousand
Gram or so, and the application aluminium oxide is instead of partial nitridation boron filler, the cost for preparing nucleocapsid heat filling is about 500 yuan every
Kilogram, so preparing nucleocapsid heat filling in the invention reduces 50-70% or so than only adding the cost of boron nitride filler.To sum up,
The present invention provides a kind of high thermal conductivity Kaptons and preparation method thereof of core-shell structure heat filling preparation.
Detailed description of the invention
Fig. 1 is the scanning electron microscope (SEM) photograph for preparing boron nitride coated aluminum oxide heat filling；
Fig. 1 is shown using electrostatic self-assembled method, prepares boron nitride coated aluminum oxide, and and boron nitride polyimide-based
Internal portion forms the heat conduction network of isolation.
Specific embodiment
The present invention is further described by the following examples, but is not limitation of the present invention.
Nucleocapsid heat filling is prepared, preparation method includes the following steps:
(1) it prepares the modified aluminium oxide of KH550: configuring dispersion liquid by the volume ratio of 1:5 with dehydrated alcohol and deionized water
500ml, it is 5 that glacial acetic acid, which is added dropwise, and adjusts the PH of dispersion liquid, 4.3g KH550 is slowly added dropwise into dispersion liquid, mechanical stirring 2h makes
KH550 hydrolysis, adds 20g aluminium oxide, 60 DEG C of heating water bath 2h, and the modified oxidation of KH550 is made in centrifugal drying after reaction
Aluminium；
(2) the modified boron nitride of preparation: weighing 20g boron nitride and be put into Muffle furnace, and temperature programming, 900 DEG C of air atmospheres are arranged
2h is calcined, using deionized water as dispersion liquid, to centrifugal drying after calcined boron nitride ultrasound 2h, modified boron nitride is made；
(3) it prepares the aluminium oxide of boron nitride cladding: weighing boron nitride modified made from step (2), deionized water, configuration is added
Concentration be 4mg/ml boron nitride dispersion, ultrasonic 1h, then be added dropwise glacial acetic acid adjust boron nitride dispersion PH be 4 after, be added
The mass ratio of the obtained KH550 of step (1) modified aluminium oxide, modified boron nitride and modified aluminium oxide is 1:5, mechanical stirring
Centrifugal drying after 2h, is made the nucleocapsid heat filling of the aluminium oxide of boron nitride cladding, and the nucleocapsid of the aluminium oxide of boron nitride cladding is led
The scanning electron microscope (SEM) photograph of hot filler is as shown in Figure 1, the boron nitride of sheet is coated on spherical oxidation it can be seen from scanning electron microscope (SEM) photograph
On aluminium, the nucleocapsid heat filling and boron nitride can cooperatively form heat conduction network structure in polyimide matrix.
Embodiment 1
A kind of preparation method of high thermal conductivity Kapton, includes the following steps:
(1) 3.15g boron nitride is added to ultrasonic 2 hours in the DMAC dispersion liquid of 82g, adds 8.615g ODA, machinery stirs
Mixing dissolves boron nitride, is made containing the reaction dissolvent after the removing of boron nitride ultrasound；
(2) 9.385g PMDA points are added in the reaction dissolvent that step (1) obtains for 50%, 20%, 20%, 8% 4 time, between each
Every 0.5h, remaining 2% PDMA regulation system viscosity makes its system viscosity reach 50000 MPas, is made and contains boron nitride
Polyamic acid solution；
(3) polyamic acid containing boron nitride made from the heat filling addition step by 3.15g boron nitride coated aluminum oxide is molten
In liquid, mechanical stirring 3h or so is put into vacuum drying oven, carries out defoaming treatment under -1Mpa；
(4) plastic film mulch is carried out with the polyamic acid solution of defoaming treatment, the film completed will be laid with and be put into the hot imines of high temperature oven
Change, the heating rate that baking oven is arranged is 2 DEG C/min, since room temperature, 20min is kept the temperature after every 40 DEG C of the raising of baking oven, until temperature
350 DEG C, after complete hot imidization are reached, cooling obtains high thermal conductivity Kapton.
Kapton obtained is carried out to the test of heating conduction with laser flash method, is led in its face of the film
Hot coefficient is 4.13 W(mK)-1, thermal coefficient is 0.55 W(mK outside face)-1。
Embodiment 2
A kind of preparation method of high thermal conductivity Kapton, includes the following steps:
(1) 4.2g boron nitride is added to ultrasonic 2 hours in the DMAC dispersion liquid of 82g, adds 8.615g ODA, mechanical stirring
Boron nitride is dissolved, is made containing the reaction dissolvent after the removing of boron nitride ultrasound；
(2) 9.385g PMDA points are added in the reaction dissolvent that step (1) obtains for 50%, 20%, 20%, 8% 4 time, between each
Every 0.5h, remaining 2% PDMA regulation system viscosity makes its system viscosity reach 50000 MPas, is made and contains boron nitride
Polyamic acid solution；
(3) polyamic acid solution containing boron nitride made from step is added in the heat filling of 2.1g boron nitride coated aluminum oxide
In, mechanical stirring 3h or so is put into vacuum drying oven, carries out defoaming treatment under -1Mpa；
(4) plastic film mulch is carried out with the polyamic acid solution of defoaming treatment, the film completed will be laid with and be put into the hot imines of high temperature oven
Change, the heating rate that baking oven is arranged is 2 DEG C/min, since room temperature, 20min is kept the temperature after every 40 DEG C of the raising of baking oven, until temperature
350 DEG C, after complete hot imidization are reached, cooling obtains high thermal conductivity Kapton.
Kapton obtained is carried out to the test of heating conduction with laser flash method, is led in its face of the film
Hot coefficient is 3.92 W(mK)-1, thermal coefficient is 0.53 W(mK outside face)-1。
Embodiment 3
A kind of preparation method of high thermal conductivity Kapton, includes the following steps:
(1) 4.725g boron nitride is added to ultrasonic 2 hours in the DMAC dispersion liquid of 82g, adds 8.615g ODA, machinery stirs
Mixing dissolves boron nitride, is made containing the reaction dissolvent after the removing of boron nitride ultrasound；
(2) 9.385g PMDA points are added in the reaction dissolvent that step (1) obtains for 50%, 20%, 20%, 8% 4 time, between each
Every 0.5h, remaining 2% PDMA regulation system viscosity makes its system viscosity reach 50000 MPas, is made and contains boron nitride
Polyamic acid solution；
(3) polyamic acid containing boron nitride made from the heat filling addition step by 1.575g boron nitride coated aluminum oxide is molten
In liquid, mechanical stirring 3h or so is put into vacuum drying oven, carries out defoaming treatment under -1Mpa；
(4) plastic film mulch is carried out with the polyamic acid solution of defoaming treatment, the film completed will be laid with and be put into the hot imines of high temperature oven
Change, the heating rate that baking oven is arranged is 2 DEG C/min, since room temperature, 20min is kept the temperature after every 40 DEG C of the raising of baking oven, until temperature
350 DEG C, after complete hot imidization are reached, cooling obtains high thermal conductivity Kapton.
Kapton obtained is carried out to the test of heating conduction with laser flash method, is led in its face of the film
Hot coefficient is 4.02 W(mK)-1, thermal coefficient is 0.47 W(mK outside face)-1。
Embodiment 4
A kind of preparation method of high thermal conductivity Kapton, includes the following steps:
(1) 1.26g boron nitride is added to ultrasonic 2 hours in the DMAC dispersion liquid of 82g, adds 8.615g ODA, machinery stirs
Mixing dissolves boron nitride, is made containing the reaction dissolvent after the removing of boron nitride ultrasound；
(2) 9.385g PMDA points are added in the reaction dissolvent that step (1) obtains for 50%, 20%, 20%, 8% 4 time, between each
Every 0.5h, remaining 2% PDMA regulation system viscosity makes its system viscosity reach 50000 MPas, is made and contains boron nitride
Polyamic acid solution；
(3) polyamic acid containing boron nitride made from the heat filling addition step by 5.04g boron nitride coated aluminum oxide is molten
In liquid, mechanical stirring 3h or so is put into vacuum drying oven, carries out defoaming treatment under -1Mpa；
(4) plastic film mulch is carried out with the polyamic acid solution of defoaming treatment, the film completed will be laid with and be put into the hot imines of high temperature oven
Change, the heating rate that baking oven is arranged is 2 DEG C/min, since room temperature, 20min is kept the temperature after every 40 DEG C of the raising of baking oven, until temperature
350 DEG C, after complete hot imidization are reached, cooling obtains high thermal conductivity Kapton.
Kapton obtained is carried out to the test of heating conduction with laser flash method, is led in its face of the film
Hot coefficient is 4.32 W(mK)-1, thermal coefficient is 0.61 W(mK outside face)-1。
Embodiment 5
A kind of preparation method of high thermal conductivity Kapton, includes the following steps:
(1) 1.08g boron nitride is added to ultrasonic 2 hours in the DMAC dispersion liquid of 82g, adds 8.615g ODA, machinery stirs
Mixing dissolves boron nitride, is made containing the reaction dissolvent after the removing of boron nitride ultrasound；
(2) 9.385g PMDA points are added in the reaction dissolvent that step (1) obtains for 50%, 20%, 20%, 8% 4 time, between each
Every 0.5h, remaining 2% PDMA regulation system viscosity makes its system viscosity reach 50000 MPas, is made and contains boron nitride
Polyamic acid solution；
(3) polyamic acid containing boron nitride made from the heat filling addition step by 4.32g boron nitride coated aluminum oxide is molten
In liquid, mechanical stirring 3h or so is put into vacuum drying oven, carries out defoaming treatment under -1Mpa；
(4) plastic film mulch is carried out with the polyamic acid solution of defoaming treatment, the film completed will be laid with and be put into the hot imines of high temperature oven
Change, the heating rate that baking oven is arranged is 2 DEG C/min, since room temperature, 20min is kept the temperature after every 40 DEG C of the raising of baking oven, until temperature
350 DEG C, after complete hot imidization are reached, cooling obtains high thermal conductivity Kapton.
Kapton obtained is carried out to the test of heating conduction with laser flash method, is led in its face of the film
Hot coefficient is 4.62 W(mK)-1, thermal coefficient is 0.69 W(mK outside face)-1。
Kapton made from product and embodiment 1-5 to domestic and international thermally conductive polyimides uses laser flash method
The test comparison of heating conduction is carried out, the Kapton that the present invention prepares has high thermal conductivity coefficient.Due to h- in the market
The price ratio Al of BN raw material2O3The price of raw material is many out, so the laminated film can be in the feelings for promoting certain heating conduction
Under condition, and increased costs profit can be reduced in processing technology.Film of the invention has preferable application neck at present
Domain and the biggish market space.
Claims (9)
1. a kind of core-shell structure heat filling, which is characterized in that the core-shell structure heat filling is by modifier treatment oxygen
Change aluminium and high-temperature calcination boron nitride, using boron nitride coated aluminum oxide made from electrostatic self-assembled method.
2. a kind of core-shell structure heat filling according to claim 1, which is characterized in that the aluminium oxide pattern is ball
Shape, partial size 1-30um；Boron nitride is hexagonal boron nitride, partial size 50nm-5um.
3. a kind of core-shell structure heat filling according to claim 1, which is characterized in that the heat filling, system
Preparation Method includes the following steps:
1) it prepares the modified aluminium oxide of KH550: configuring dispersion liquid with dehydrated alcohol and deionized water, wherein the quality of dehydrated alcohol
Concentration is 5-60%, and adjusting PH is 5-6, and KH550 is slowly added dropwise into dispersion liquid, and wherein the mass parts of KH550 are the 1- of dispersion liquid
5%；Stirring hydrolysis, adds aluminium oxide, and wherein the mass parts of aluminium oxide are the 10-60% of dispersion liquid, is centrifuged after heating water bath dry
It is dry, the modified aluminium oxide of KH550 is made；
2) the modified boron nitride of preparation: weighing boron nitride, is point with deionized water after calcining 1-2h under 900-1200 DEG C of environment
Dispersion liquid, centrifugal drying after ultrasound, is made modified boron nitride；
3) aluminium oxide of boron nitride cladding is prepared: the ratio that the mass ratio by modified boron nitride and modified aluminium oxide is 1:1-10
Example weighs boron nitride modified made from step (2), and deionized water is added, and the boron nitride that configuration concentration is 1-10mg/ml disperses
Liquid, it is 4-5 that PH is adjusted after ultrasonic, step (1) is added, the aluminium oxide that KH550 is modified is made, stir centrifugal drying, boron nitride is made
The nucleocapsid heat filling of the aluminium oxide of cladding.
4. a kind of high thermal conductivity Kapton prepared with core-shell structure heat filling, which is characterized in that by following mass parts
The raw material of proportion is prepared, the heat filling including 10-50 mass parts, the modifying agent of 1-5 mass parts, 80-500 mass parts
Polyamic acid solution；
The heat filling is core-shell structure heat filling.
5. a kind of high thermal conductivity Kapton prepared with core-shell structure heat filling according to claim 4, special
Sign is that the modifying agent is Silane coupling agent KH550.
6. a kind of high thermal conductivity Kapton prepared with core-shell structure heat filling according to claim 4, special
Sign is that the polyamic acid solution after being dissolved in organic solvent by diamine, then dibasic anhydride system is added into diamine solution
；The mass ratio of the material of dibasic anhydride and diamine is 1:1-1.05, and polyamic acid solution mass concentration is 15-25%.
7. a kind of high thermal conductivity Kapton prepared with core-shell structure heat filling according to claim 4, special
Sign is that the dibasic anhydride is pyromellitic acid dianhydride (PMDA), 3,3,, 4,4,Bibenzene tetracarboxylic dianhydride, 2,3,, 3,4,Biphenyl
Tetracarboxylic acid dianhydride, 3,3,, 4,4,Benzophenone tetracarboxylic dianhydride, 2,3,, 6,7,One of naphthalenetetracarbacidic acidic dianhydride；
The diamine is p-phenylenediamine, m-phenylene diamine (MPD), benzidine, 4,4,Diaminodiphenyl ether, p dimethylamine, 3,
4,Diaminodiphenyl ether, 4,4,Diaminodiphenyl-methane, 3,3,One kind of dimethoxy benzidine；
The organic solvent is n,N-dimethylacetamide, n,N-Dimethylformamide, N-Methyl pyrrolidone, dimethyl second
One of amide, dimethyl sulfoxide.
8. a kind of high thermal conductivity Kapton according to claim 4, which is characterized in that the film, with a thickness of
10-500um。
9. a kind of preparation method for material of the high thermal conductivity Kapton prepared with core-shell structure heat filling, which is characterized in that
Include the following steps:
1) it prepares the modified aluminium oxide of KH550: configuring dispersion liquid with dehydrated alcohol and deionized water, wherein the quality of dehydrated alcohol
Concentration is 5-60%, and adjusting PH is 5-6, and KH550 is slowly added dropwise into dispersion liquid, and wherein the mass parts of KH550 are the 1- of dispersion liquid
5%；Stirring hydrolysis, adds aluminium oxide, and wherein the mass parts of aluminium oxide are the 10-60% of dispersion liquid, is centrifuged after heating water bath dry
It is dry, the modified aluminium oxide of KH550 is made；
2) the modified boron nitride of preparation: weighing boron nitride, is point with deionized water after calcining 1-2h under 900-1200 DEG C of environment
Dispersion liquid, centrifugal drying after ultrasound, is made modified boron nitride；
3) aluminium oxide of boron nitride cladding is prepared: the ratio that the mass ratio by modified boron nitride and modified aluminium oxide is 1:1-10
Example weighs boron nitride modified made from step 2, and deionized water is added, and the boron nitride that configuration concentration is 1-10mg/ml disperses
Liquid, it is 4-5 that PH is adjusted after ultrasonic, step 1) is added, the aluminium oxide that KH550 is modified is made, stir centrifugal drying, boron nitride is made
The nucleocapsid heat filling of coated aluminum oxide；
4) after boron nitride being uniformly dispersed in organic dispersions, diamine dissolution is added, then dibasic anhydride system is added into solution
, the polyamic acid solution containing boron nitride is made；
5) nucleocapsid heat filling made from step 3) is added in the polyamic acid solution containing boron nitride made from step 4) and is stirred
After mixing uniformly, vacuum defoaming treatment；
6) plastic film mulch is carried out with the polyamic acid solution of defoaming treatment, the film completed will be laid with and carry out hot imidization processing, it is complete
After full hot imidization, cooling obtains high thermal conductivity Kapton.
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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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