CN109438735B - High-thermal-conductivity polyimide-based composite film and preparation method thereof - Google Patents
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Abstract
The invention discloses a preparation method of a polyimide-based composite film with high thermal conductivity, which comprises the following steps: adding inorganic heat-conducting filler and polyethylene glycol diamine into an organic polar solvent, and uniformly stirring and dispersing the mixture by a sand mill to obtain an inorganic heat-conducting filler dispersion liquid with the surface modified by the polyethylene glycol diamine; adding aromatic diamine into the inorganic heat-conducting filler dispersion liquid to form a diamine solution; adding aromatic dianhydride into diamine solution in batches under stirring, carrying out polycondensation reaction on polyethylene glycol diamine, aromatic diamine and aromatic dianhydride to form a polyamic acid resin solution, defoaming in vacuum, and imidizing to obtain the polyimide film with high thermal conductivity. According to the invention, the modification of the inorganic filler is realized without introducing a third additive, the modified inorganic composite filler is more uniformly dispersed in the matrix, the heat-conducting property of the film is more stable, the mechanical property of the film is more uniform, the anisotropy of the film is reduced, the process is simple, and the industrial production is easy.
Description
Technical Field
The invention belongs to the technical field of high-thermal-conductivity polymer films, and particularly relates to a high-thermal-conductivity polyimide-based composite 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 devices enable a circuit or a chip to rapidly accumulate heat in a very small limited space, and whether the circuit or the chip can dissipate heat in time becomes a key that affects the service life, the operation stability and the safety performance of components, and the heat consumption generated by electronic components is considered to be one of the key problems to be solved urgently.
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, the high thermal conductivity polyimide film is prepared by filling a large amount of inorganic thermal conductive filler in a polyimide matrix in an organic-inorganic composite mode to realize the high thermal conductivity coefficient of the polyimide film, and the material obtained by the method has better thermal conductivity, low price and easy industrial production, and is the main direction of the research on the high thermal conductivity polyimide film at present. However, when the amount of the filler dispersed in the resin is large, the heat conductivity of the film is improved, but the comprehensive properties, especially the mechanical properties of the film are remarkably reduced, even the film cannot be cast and stretched into a film, and the industrial production cannot be realized, which has a great problem in practical application.
Disclosure of Invention
The invention aims to overcome the defects and shortcomings, provides an organic-inorganic composite polyimide film with high thermal conductivity coefficient, excellent comprehensive performance and easy realization of industrial production, and a preparation method thereof.
In order to solve the technical problems, the technical scheme provided by the invention is as follows: the polyimide-based composite film with high thermal conductivity comprises a polyimide matrix and inorganic thermal conductive fillers uniformly distributed in the polyimide matrix, wherein the structural formula of the polyimide matrix comprises a structural unit A and a structural unit B;
wherein, the structural formula of the structural unit A is as follows:
the structural formula of the structural unit B is as follows:
wherein Ar represents a residue of an aromatic dianhydride (aromatic dianhydride aromatic moiety); ar' a residue of an aromatic diamine (aromatic moiety of the aromatic diamine); n is an integer of 1 to 85.
The invention selects the polyethylene glycol diamine as the surface modifier of the inorganic heat-conducting filler and one of the diamine monomers as the polyimide raw material, so that the polyimide matrix has A, B two structural units, meanwhile, the A structural unit is an aromatic structure and can improve the overall thermal stability of the matrix, and the diamine monomer in the B structural unit plays a role of a main chain structure and the surface modifier, thereby improving the organic-inorganic combination property, improving the dispersibility of the inorganic filler, improving the overall performance of the film, and avoiding the possibility that the material is possibly deformed due to the introduction of a third additive.
Preferably, the structural formula of the polyimide substrate is composed of a structural unit A and a structural unit B.
Preferably, the structural formula of the polyimide matrix contains x structural units A and y structural units B, x is an integer from 1 to 100, y is an integer from 1 to 1000, and x: y is preferably 1:20 to 100.
Preferably, the aromatic dianhydride is one selected from pyromellitic dianhydride (PMDA), 3,3',4,4' -biphenyltetracarboxylic dianhydride (s-BPDA), 2,3,3',4' -biphenyltetracarboxylic dianhydride (α -BPDA), 2,3,3',4' -diphenylethertetracarboxylic dianhydride (α -OPDA), 3,3',4,4' -diphenylethertetracarboxylic dianhydride (s-OPDA), 3,3',4,4' -benzophenonetetracarboxylic dianhydride (BTDA), and bisphenol a type diether dianhydride (BPADA).
Preferably, the aromatic diamine is selected from one of 4,4 '-diaminodiphenyl ether (ODA), 3, 4' -diaminodiphenyl ether, p-phenylenediamine, o-phenylenediamine and m-phenylenediamine, 2-bis [4- (4-aminophenoxy) phenyl ] propane.
Preferably, the inorganic heat-conducting filler accounts for 20-60% of the total mass of the high heat-conducting polyimide film; more preferably 30% to 50%.
Preferably, the inorganic heat-conducting filler is one or more of alpha-crystal-form alumina with the particle size of 0.1-5 mu m, hexagonal boron nitride or aluminum nitride. More preferably alpha crystal form alumina or hexagonal boron nitride with the grain diameter of 1-2 mu m.
The invention takes polyethylene glycol diamine as the surface modifier of the inorganic heat-conducting filler and the raw material of the polyimide monomer, and the polyimide film with high heat conductivity is prepared by carrying out imidization on the inorganic heat-conducting filler after carrying out surface modification on the inorganic heat-conducting filler, and carrying out polycondensation reaction on the inorganic heat-conducting filler, aromatic diamine and aromatic dianhydride.
The invention also provides a preparation method of the polyimide-based composite film with high thermal conductivity, which comprises the following steps:
1) adding inorganic heat-conducting filler and polyethylene glycol diamine into an organic polar solvent, and uniformly stirring and dispersing the mixture by a sand mill to obtain an inorganic heat-conducting filler dispersion liquid with the surface modified by the polyethylene glycol diamine;
the structural formula of the polyethylene glycol diamine is as follows:
wherein n is an integer from 1 to 85;
2) adding aromatic diamine into the inorganic heat-conducting filler dispersion liquid obtained in the step 1) to form a diamine solution;
3) adding aromatic dianhydride into the diamine solution obtained in the step 2) in batches under stirring, and carrying out polycondensation reaction on polyethylene glycol diamine, aromatic diamine and aromatic dianhydride to form a polyamic acid solution;
4) defoaming the polyamic acid resin solution obtained in the step 3) in vacuum, and imidizing to obtain the high-thermal-conductivity polyimide film.
Preferably, the organic polar solvent is one or more of N-methylpyrrolidone, N-dimethylformamide and N, N-dimethylacetamide.
Preferably, the molar ratio of the total amount of diamine (polyethylene glycol diamine + aromatic diamine) to the total amount of dianhydride is 1:0.95 to 1.1. And the polyethylene glycol diamine accounts for 0.5-10%, preferably 1-5% of the total molar weight of the diamine.
Preferably, the operation temperature in the step 2) is-15 to 30 ℃.
In the step 4), imidization refers to thermal imidization, or chemical imidization after adding an accelerant and a dehydrating agent to be uniformly mixed to obtain the high-thermal-conductivity polyimide film.
The hot-pressing amination temperature is 100-400 ℃ and the temperature programming is used for imidization; the chemical imidization dehydrating agent is one or more selected from trifluoroacetic anhydride, acetic anhydride, propionic anhydride, aromatic monocarboxylic anhydride and acetyl chloride; the chemical imidization method accelerant is selected from one or more of pyridine, beta-pyrroline, lutidine, collidine, quinoline, isoquinoline, triethylamine and N, N-dimethylethanolamine.
Compared with the prior art, the invention has the advantages that:
(1) the invention selects the polyethylene glycol diamine as the surface modifier of the inorganic heat-conducting filler and one of the diamine monomers as the polyimide raw material, the C-O, C-H in the polyethylene glycol chain segment in the selected polyethylene glycol diamine molecular chain has high polarity, and simultaneously the serpentine structure of the molecular chain and the-OH bond on the surface of the inorganic heat-conducting filler establish stronger hydrogen bond, so that the inorganic heat-conducting filler forms steric hindrance effect, the surface modification effect is achieved, the agglomeration phenomenon of alumina particles is reduced, meanwhile, the amino group in the polyethylene glycol diamine, the aromatic diamine and the aromatic dianhydride form ternary polyamic acid through polycondensation reaction, the inorganic agglomeration phenomenon is greatly reduced, the stability of the combination of the inorganic heat-conducting filler and a PI matrix is improved, and the comprehensive performance of the high heat-conducting polyimide film under the doping of the high inorganic heat-conducting filler is improved, especially, the mechanical property is more beneficial to casting and stretching film forming, thereby realizing industrialized production.
(2) According to the invention, the modification of the inorganic filler is realized without introducing a third additive, the modified inorganic composite filler is more uniformly dispersed in the matrix, the heat-conducting property of the film is more stable, the mechanical property of the film is more uniform, the anisotropy of the film is reduced, the process is simple, and the industrial production is easy.
(3) The invention does not need to introduce an auxiliary agent except for the non-polyimide monomer raw material, reduces the film cost, and avoids the influence of the introduction of the auxiliary agent on the reduction of the comprehensive properties of the film, such as machinery, electricity and the like.
(4) The preparation method is simple and easy to realize industrial production.
Detailed Description
In order to facilitate an understanding of the present invention, the present invention will be described more fully and in detail with reference to the preferred embodiments, but the scope of the present invention is not limited to the specific embodiments below.
Unless otherwise defined, all terms of art used hereinafter have the same meaning as commonly understood by one of ordinary skill in the art. The terminology used herein is for the purpose of describing particular embodiments only and is not intended to limit the scope of the present invention.
Unless otherwise specifically stated, various raw materials, reagents, instruments, equipment and the like used in the present invention are commercially available or can be prepared by existing methods.
Example 1:
a high-thermal-conductivity polyimide-based composite film comprises a polyimide matrix and inorganic thermal-conductivity filler alpha-crystal alumina uniformly distributed in the polyimide matrix, wherein the inorganic thermal-conductivity filler accounts for 35% of the total mass of the high-thermal-conductivity polyimide film; the structural formula of the polyimide substrate comprises 1-15 structural units A and 150-200 structural units B,
wherein, the structural formula of the structural unit A is as follows:
the structural formula of the structural unit B is as follows:
wherein Ar represents a residue of pyromellitic dianhydride; ar 'is the residue of 4,4' -diaminodiphenyl ether; n is about 3 or 4.
In the embodiment, the polyimide-based composite film with high thermal conductivity is prepared by using polyethylene glycol diamine as an inorganic filler thermal conductivity surface modifier and a polyimide monomer as raw materials, and performing polycondensation reaction on the modified inorganic thermal conductivity filler surface, aromatic diamine and aromatic dianhydride to prepare the polyimide film with high thermal conductivity, wherein the preparation method comprises the following steps:
(1) mixing 11.26g of 1 micron alpha crystal form alumina inorganic heat-conducting filler and 0.5g of polyethylene glycol diamine (NH)2-PEG(200)-NH2) Adding the mixture into 182.3g of N, N-dimethylformamide solvent, and uniformly stirring and dispersing the mixture at a high speed by a sand mill to obtain inorganic heat-conducting filler dispersion liquid after the surface of the polyethanediol diamine is modified;
(2) adding 9.5g of ODA aromatic diamine into the inorganic heat-conducting filler dispersion liquid obtained in the step (1), and stirring and dissolving at-15 ℃ to form a diamine solution;
(3) 10.91g of PMDA aromatic dianhydride was added in portions to the diamine solution of step (2) under stirring, NH2-PEG(200)-NH2Performing polycondensation reaction on the ODA and the PMDA to form a ternary polyamic acid resin solution;
(4) and (3) defoaming the polyamic acid resin solution obtained in the step (3) in vacuum, adding 10g of triethylamine accelerator and 20g of acetic anhydride dehydrating agent, uniformly mixing, salivating to form a film, and heating to perform imidization completely by using a program temperature of 100-450 ℃ (100 ℃/10min,150 ℃/10min,200 ℃/10min,250 ℃/10min,300 ℃/5min,350 ℃/3min and 400 ℃/2min) to obtain the high-thermal-conductivity polyimide film.
Example 2:
a high-thermal-conductivity polyimide-based composite film comprises a polyimide matrix and inorganic thermal-conductivity filler alpha-crystal alumina uniformly distributed in the polyimide matrix, wherein the inorganic thermal-conductivity filler accounts for 35% of the total mass of the high-thermal-conductivity polyimide film; the structural formula of the polyimide substrate comprises 1-15 structural units A and 150-200 structural units B,
wherein, the structural formula of the structural unit A is as follows:
the structural formula of the structural unit B is as follows:
wherein Ar represents a residue of pyromellitic dianhydride; ar 'is the residue of 4,4' -diaminodiphenyl ether; n is about 8 or 9.
The polyimide-based composite film with high thermal conductivity is prepared by taking polyethylene glycol diamine as an inorganic filler thermal conductivity surface modifier and a polyimide monomer raw material, carrying out surface modification on the inorganic thermal conductivity filler, and then carrying out polycondensation reaction on the inorganic thermal conductivity filler, aromatic diamine and aromatic dianhydride, wherein the preparation method comprises the following steps:
(1) 11.53g of alpha crystal form alumina inorganic heat-conducting filler with the particle diameter of 1 mu m and 1g of polyethylene glycol diamine (NH)2-PEG(400)-NH2) Adding the mixture into 182.3g of N, N-dimethylformamide solvent, and uniformly stirring and dispersing the mixture at a high speed by a sand mill to obtain inorganic heat-conducting filler dispersion liquid after the surface of the polyethanediol diamine is modified;
(2) adding 9.5g of ODA aromatic diamine into the inorganic heat-conducting filler dispersion liquid obtained in the step (1), and stirring and dissolving at-20 ℃ to form a diamine solution;
(3) adding 10.91g of PMDA aromatic dianhydride in portions into the diamine solution obtained in the step (2) under stirring, and adding NH2-PEG(400)-NH2Performing polycondensation reaction on the ODA and the PMDA to form a ternary polyamic acid resin solution;
(4) and (3) defoaming the polyamic acid resin solution obtained in the step (3) in vacuum, adding 10g of triethylamine accelerator and 20g of acetic anhydride dehydrating agent, uniformly mixing, salivating to form a film, and heating to perform imidization completely by using a program temperature of 100-450 ℃ (100 ℃/10min,150 ℃/10min,200 ℃/10min,250 ℃/10min,300 ℃/5min,350 ℃/3min and 400 ℃/2min) to obtain the high-thermal-conductivity polyimide film.
Example 3:
a high-thermal-conductivity polyimide-based composite film comprises a polyimide matrix and inorganic thermal-conductivity filler alpha-crystal alumina uniformly distributed in the polyimide matrix, wherein the inorganic thermal-conductivity filler accounts for 35% of the total mass of the high-thermal-conductivity polyimide film; the structural formula of the polyimide substrate comprises 1-15 structural units A and 150-200 structural units B,
wherein, the structural formula of the structural unit A is as follows:
the structural formula of the structural unit B is as follows:
wherein Ar represents a residue of pyromellitic dianhydride; ar 'is the residue of 4,4' -diaminodiphenyl ether; n is about 16 or 17.
The polyimide-based composite film with high thermal conductivity is prepared by taking polyethylene glycol diamine as an inorganic filler thermal conductivity surface modifier and a polyimide monomer raw material, carrying out surface modification on the inorganic thermal conductivity filler, and then carrying out polycondensation reaction on the inorganic thermal conductivity filler, aromatic diamine and aromatic dianhydride, wherein the preparation method comprises the following steps:
(1) 12.07g of alpha crystal form alumina inorganic heat-conducting filler with the grain diameter of 1 micron and 2g of polyethylene glycol diamine (NH)2-PEG(800)-NH2) Adding the mixture into 182.3g of N, N-dimethylformamide solvent, and uniformly stirring and dispersing the mixture at a high speed by a sand mill to obtain inorganic heat-conducting filler dispersion liquid after the surface of the polyethanediol diamine is modified;
(2) adding 9.5g of ODA aromatic diamine into the inorganic heat-conducting filler dispersion liquid obtained in the step (1), and stirring and dissolving at the temperature of-10 ℃ to form a diamine solution;
(3) adding 10.91g of PMDA aromatic dianhydride in portions into the diamine solution obtained in the step (2) under stirring, and adding NH2-PEG(800)-NH2Performing polycondensation reaction on the ODA and the PMDA to form a ternary polyamic acid resin solution;
(4) and (3) defoaming the polyamic acid resin solution obtained in the step (3) in vacuum, adding 10g of triethylamine accelerator and 20g of acetic anhydride dehydrating agent, uniformly mixing, salivating to form a film, and heating to perform imidization completely by using a program temperature of 100-450 ℃ (100 ℃/10min,150 ℃/10min,200 ℃/10min,250 ℃/10min,300 ℃/5min,350 ℃/3min and 400 ℃/2min) to obtain the high-thermal-conductivity polyimide film.
Example 4:
a high-thermal-conductivity polyimide-based composite film comprises a polyimide matrix and inorganic thermal-conductivity filler alpha-crystal alumina uniformly distributed in the polyimide matrix, wherein the inorganic thermal-conductivity filler accounts for 35% of the total mass of the high-thermal-conductivity polyimide film; the structural formula of the polyimide substrate comprises 1-15 structural units A and 150-200 structural units B,
wherein, the structural formula of the structural unit A is as follows:
the structural formula of the structural unit B is as follows:
wherein Ar represents a residue of 3,3',4,4' -diphenylether tetracarboxylic dianhydride; ar 'is the residue of 4,4' -diaminodiphenyl ether; n is about 8 or 9.
The polyimide-based composite film with high thermal conductivity is prepared by taking polyethylene glycol diamine as an inorganic filler thermal conductivity surface modifier and a polyimide monomer raw material, carrying out surface modification on the inorganic thermal conductivity filler, and then carrying out polycondensation reaction on the inorganic thermal conductivity filler, aromatic diamine and aromatic dianhydride, wherein the preparation method comprises the following steps:
(1) 11.58g of alpha crystal form alumina inorganic heat-conducting filler with the particle size of 1 micron and 1.2g of polyethylene glycol diamine (NH)2-PEG(400)-NH2) Adding the mixture into 182.3g of N, N-dimethylformamide solvent, and uniformly stirring and dispersing the mixture at a high speed by a sand mill to obtain inorganic heat-conducting filler dispersion liquid after the surface of the polyethanediol diamine is modified;
(2) adding 9.4g of ODA aromatic diamine into the inorganic heat-conducting filler dispersion liquid obtained in the step (1), and stirring and dissolving at the temperature of-5 ℃ to form a diamine solution;
(3) 10.91gAdding the PMDA aromatic dianhydride to the diamine solution obtained in the step (2) in batches under stirring, and adding NH2-PEG(400)-NH2Performing polycondensation reaction on the ODA and the s-ODPA to form a ternary polyamic acid resin solution;
(4) and (3) defoaming the polyamic acid resin solution obtained in the step (3) in vacuum, adding 10g of triethylamine accelerator and 20g of acetic anhydride dehydrating agent, uniformly mixing, salivating to form a film, and heating to perform imidization completely by using a program temperature of 100-450 ℃ (100 ℃/10min,150 ℃/10min,200 ℃/10min,250 ℃/10min,300 ℃/5min,350 ℃/3min and 400 ℃/2min) to obtain the high-thermal-conductivity polyimide film.
Example 5:
a high-thermal-conductivity polyimide-based composite film comprises a polyimide matrix and hexagonal boron nitride which is an inorganic thermal-conductivity filler and uniformly distributed in the polyimide matrix, wherein the inorganic thermal-conductivity filler accounts for 50% of the total mass of the high-thermal-conductivity polyimide film; the structural formula of the polyimide substrate comprises 1-15 structural units A and 150-200 structural units B,
wherein, the structural formula of the structural unit A is as follows:
the structural formula of the structural unit B is as follows:
wherein Ar represents a residue of pyromellitic dianhydride; ar 'is the residue of 4,4' -diaminodiphenyl ether; n is about 3 or 4.
The polyimide-based composite film with high thermal conductivity is prepared by taking polyethylene glycol diamine as an inorganic filler thermal conductivity surface modifier and a polyimide monomer raw material, carrying out surface modification on the inorganic thermal conductivity filler, and then carrying out polycondensation reaction on the inorganic thermal conductivity filler, aromatic diamine and aromatic dianhydride, wherein the preparation method comprises the following steps:
(1) 20.91g of hexagonal boron nitride inorganic heat-conducting filler with the particle size of 1 micron and 0.5g of polyethylene glycol diamine (NH)2-PEG(200)-NH2) Adding 182.3g of N, N-dimethylformylStirring and dispersing the amine solvent uniformly 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 9g of ODA aromatic diamine into the inorganic heat-conducting filler dispersion liquid obtained in the step (1), and stirring and dissolving at the temperature of-15 ℃ to form a diamine solution;
(3) adding 10.91g of PMDA aromatic dianhydride in portions into the diamine solution obtained in the step (2) under stirring, and adding NH2-PEG(200)-NH2Performing polycondensation reaction on the ODA and the PMDA to form a ternary polyamic acid resin solution;
(4) and (3) defoaming the polyamic acid resin solution obtained in the step (3) in vacuum, adding 10g of triethylamine accelerator and 20g of acetic anhydride dehydrating agent, uniformly mixing, salivating to form a film, and heating to perform imidization completely by using a program temperature of 100-450 ℃ (100 ℃/10min,150 ℃/10min,200 ℃/10min,250 ℃/10min,300 ℃/5min,350 ℃/3min and 400 ℃/2min) to obtain the high-thermal-conductivity polyimide film.
Example 6:
a high-thermal-conductivity polyimide-based composite film comprises a polyimide matrix and hexagonal boron nitride which is an inorganic thermal-conductivity filler and uniformly distributed in the polyimide matrix, wherein the inorganic thermal-conductivity filler accounts for 50% of the total mass of the high-thermal-conductivity polyimide film; the structural formula of the polyimide substrate comprises 1-15 structural units A and 150-200 structural units B,
wherein, the structural formula of the structural unit A is as follows:
the structural formula of the structural unit B is as follows:
wherein Ar represents a residue of 3,3',4,4' -diphenylether tetracarboxylic dianhydride; ar 'is the residue of 4,4' -diaminodiphenyl ether; n is about 3 or 4.
A high thermal conductivity polyimide-based composite film is prepared by taking polyethylene glycol diamine as an inorganic filler thermal conductivity surface modifier and a polyimide monomer raw material, carrying out surface modification on the inorganic thermal conductivity filler, and then carrying out polycondensation reaction on the inorganic thermal conductivity filler, aromatic diamine and aromatic dianhydride to prepare the high thermal conductivity polyimide film, wherein the preparation method comprises the following steps:
(1) 25.5g of hexagonal boron nitride inorganic heat-conducting filler with the particle size of 1 micron and 0.5g of polyethylene glycol diamine (NH)2-PEG(200)-NH2) Adding the mixture into 182.3g of N, N-dimethylformamide solvent, and uniformly stirring and dispersing the mixture at a high speed by a sand mill to obtain inorganic heat-conducting filler dispersion liquid after the surface of the polyethanediol diamine is modified;
(2) adding 9g of ODA aromatic diamine into the inorganic heat-conducting filler dispersion liquid obtained in the step (1), and stirring and dissolving at-15 ℃ to form a diamine solution;
(3) adding 15.5g of s-ODPA aromatic dianhydride in batches into the diamine solution obtained in the step (2) under stirring, and adding NH2-PEG(200)-NH2ODA and s-ODPA form a ternary polyamic acid resin solution through a polycondensation reaction
(4) And (3) defoaming the polyamic acid resin solution obtained in the step (3) in vacuum, adding 10g of triethylamine accelerator and 20g of acetic anhydride dehydrating agent, uniformly mixing, salivating to form a film, and heating to perform imidization completely by using a program temperature of 100-450 ℃ (100 ℃/10min,150 ℃/10min,200 ℃/10min,250 ℃/10min,300 ℃/5min,350 ℃/3min and 400 ℃/2min) to obtain the high-thermal-conductivity polyimide film.
Comparative example 1:
comparative example 1 differs from example 1 only in that no polyethylene glycol diamine is used, only ODA and PMDA are used as monomers, and the other steps are in accordance with the method described in example 1.
The performance test results of the polyimide films prepared in examples 1 to 6 and comparative example 1 are shown in table 1.
In table 1: the tensile strength and the elongation at break are tested by adopting an ASTM D882 standard, the electrical strength is tested by adopting an ASTM D149 standard, and the thermal conductivity is measured by adopting a thermal diffusion coefficient method.
Claims (9)
1. A high-thermal-conductivity polyimide-based composite film comprises a polyimide matrix and inorganic thermal-conductivity fillers uniformly distributed in the polyimide matrix, and is characterized in that the structural formula of the polyimide matrix comprises a structural unit A and a structural unit B;
wherein, the structural formula of the structural unit A is as follows:
；
the structural formula of the structural unit B is as follows:
；
wherein Ar represents a residue of an aromatic dianhydride; ar' a residue of an aromatic diamine; n is an integer of 1 to 85; the high-thermal-conductivity polyimide-based composite film is prepared by taking polyethylene glycol diamine as an inorganic thermal-conductivity filler surface modifier and a polyimide monomer raw material, carrying out surface modification on an inorganic thermal-conductivity filler, carrying out polycondensation reaction on the inorganic thermal-conductivity filler, and then imidizing the inorganic thermal-conductivity filler, aromatic diamine and aromatic dianhydride; the inorganic heat-conducting filler is one or more of alpha crystal form alumina with the particle size of 0.1-5 mu m, hexagonal boron nitride or aluminum nitride.
2. The polyimide-based composite film according to claim 1, wherein the polyimide matrix has a structural formula consisting of a structural unit a and a structural unit B.
3. The polyimide-based composite film according to claim 1 or 2, wherein the polyimide matrix has a structure including x structural units a and y structural units B, x is an integer of 1 to 100, and y is an integer of 1 to 1000.
4. The polyimide-based composite film according to claim 3, wherein x: y = 1: 10-200.
5. The highly thermally conductive polyimide-based composite film according to claim 1, wherein the aromatic dianhydride is one selected from the group consisting of pyromellitic dianhydride (PMDA), 3,3',4,4' -biphenyltetracarboxylic dianhydride (s-BPDA), 2,3,3',4' -biphenyltetracarboxylic dianhydride (α -BPDA), 2,3,3',4' -diphenylethertetracarboxylic dianhydride (α -OPDA), 3,3',4,4' -diphenylethertetracarboxylic dianhydride (s-OPDA), 3,3',4,4' -benzophenonetetracarboxylic dianhydride (BTDA), and bisphenol a type diether dianhydride (BPADA).
6. The highly thermally conductive polyimide-based composite film according to claim 1, wherein the aromatic diamine is one selected from the group consisting of 4,4 '-diaminodiphenyl ether, 3, 4' -diaminodiphenyl ether, p-phenylenediamine, o-phenylenediamine and m-phenylenediamine, and 2, 2-bis [4- (4-aminophenoxy) phenyl ] propane.
7. The polyimide-based composite film according to claim 1, wherein the inorganic thermally conductive filler accounts for 20 to 60% of the total mass of the polyimide film.
8. The preparation method of the polyimide-based composite film with high thermal conductivity according to any one of claims 1 to 7, comprising the steps of:
1) adding inorganic heat-conducting filler and polyethylene glycol diamine into an organic polar solvent, and uniformly stirring and dispersing the mixture by a sand mill to obtain an inorganic heat-conducting filler dispersion liquid with the surface modified by the polyethylene glycol diamine;
the structural formula of the polyethylene glycol diamine is as follows:
wherein n is an integer from 1 to 85;
2) adding aromatic diamine into the inorganic heat-conducting filler dispersion liquid obtained in the step 1) to form a diamine solution;
3) adding aromatic dianhydride into the diamine solution obtained in the step 2) in batches under stirring, and carrying out polycondensation reaction on polyethylene glycol diamine, aromatic diamine and aromatic dianhydride to form a polyamic acid solution;
4) defoaming the polyamic acid resin solution obtained in the step 3) in vacuum, and imidizing to obtain the high-thermal-conductivity polyimide film.
9. The method according to claim 8, wherein the organic polar solvent is one or more selected from the group consisting of N-methylpyrrolidone, N-dimethylformamide and N, N-dimethylacetamide.
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