CN117430949B - Polyimide film with high heat conduction and low thermal expansion coefficient and preparation method thereof - Google Patents

Polyimide film with high heat conduction and low thermal expansion coefficient and preparation method thereof Download PDF

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CN117430949B
CN117430949B CN202311612010.6A CN202311612010A CN117430949B CN 117430949 B CN117430949 B CN 117430949B CN 202311612010 A CN202311612010 A CN 202311612010A CN 117430949 B CN117430949 B CN 117430949B
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CN117430949A (en
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张帅林
陈超
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Jiangsu Jitri Smart Liquid Crystal Sci and Tech Co Ltd
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    • C08G73/06Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/10Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
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    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
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Abstract

The invention belongs to the technical field of polyimide film preparation, and provides a polyimide film with high heat conduction and low thermal expansion coefficient and a preparation method thereof, wherein the polyimide film comprises the following components in parts by weight: 5-40 parts of organic amine modified heat conducting filler, 50-120 parts of polar solvent, 2-10 parts of dianhydride and 2-12 parts of diamine, and the preparation method of the polyimide film comprises the following steps: under the protection of nitrogen, dianhydride and diamine are firstly placed in a polar solvent, uniformly stirred for polycondensation reaction at the reaction temperature of 30-50 ℃ for 30-60 minutes, then organic amine modified heat-conducting filler is added, and after stirring and ultrasonic defoaming, tape casting treatment is carried out, and finally heating and curing treatment is carried out in a vacuum drying oven. The imide film prepared by the invention has the advantages of high heat conduction and low thermal expansion coefficient, and improves the comprehensive performance and application scene of the imide film.

Description

Polyimide film with high heat conduction and low thermal expansion coefficient and preparation method thereof
Technical Field
The invention relates to the field of polyimide materials, in particular to a polyimide film with high heat conduction and low thermal expansion coefficient and a preparation method thereof.
Background
Polyimide is a highly regular polymer, and has the characteristics of excellent chemical stability, wear resistance, flame retardance, high temperature resistance, low temperature resistance, corrosion resistance, radiation resistance and the like, and therefore, polyimide also exhibits excellent mechanical properties and dielectric properties, and is widely used in various fields due to the excellent properties. In the aerospace field, polyimides are used to make high temperature structural members, thermal insulation materials, and electronic components. In the microelectronics and nanotechnology fields, polyimides can be used to make high performance electronic devices and nanomaterials. In the field of liquid crystal displays, polyimide is used as an alignment agent and an encapsulation material. In addition, polyimide is also used in the fields of separation membranes, lasers, optical devices, etc., and in summary, polyimide is widely recognized as an engineering plastic having great potential due to its excellent properties and various application fields.
With the advancement of technology, polyimide has faced challenges in the service environment of high thermal conductivity and low expansion coefficient. In particular, because polyimide molecular chains have high regularity, and their inter-molecular interactions are strong, resulting in a slower heat conduction rate, there is a need to find a suitable method to improve the thermal conductivity. In addition, the highly ordered structure of polyimide molecular chain makes it expand or contract greatly under temperature change, and the expansion coefficient needs to be reduced by controlling the process microstructure and other modes. To overcome these challenges, researchers are conducting research through approaches such as introducing thermally conductive fillers, changing molecular structures, optimizing synthesis processes and material formulations. Although the above approaches can improve the thermal conductivity and reduce the thermal expansion coefficient of polyimide to some extent, certain challenges remain, mainly in: (1) The heat conducting performance still needs to be improved, and although the introduction of the heat conducting filler can increase the heat conducting performance of polyimide, the selection and the addition amount of the heat conducting filler still need to be further optimized so as to improve the heat conducting effect. (2) The thermal expansion coefficient is poor, and the thermal expansion coefficient of polyimide is larger, so that more suitable heat conducting filler needs to be searched for to reduce the difference of the thermal expansion coefficients, for example, chinese patent publication No. CN113999414A discloses a heat conducting filler reinforced polyimide with different particle sizes and particle shapes, so that the heat conducting performance of polyimide can be improved to a certain extent, but the spherical granular heat conducting filler has a certain limitation in reducing the thermal expansion coefficient. (3) The weak interface bonding is another problem, and the heat conductive filler tends to be difficult to form a firm interface bonding with polyimide, which may lead to a reduction in heat conductive effect, as the silane coupling agent disclosed in chinese patent publication No. CN114058049a improves the interface bonding of polyimide and the heat conductive filler SiO 2, which may reduce the thermal expansion coefficient of polyimide to some extent. Therefore, future research needs to be conducted to solve these problems, and approaches such as improving selection and addition modes of the heat conducting filler, optimizing interface bonding and the like are needed to further improve the heat conducting property of polyimide and reduce the thermal expansion coefficient, so that a wider field and higher performance requirements can be provided for polyimide application.
Disclosure of Invention
The invention aims to provide a polyimide film with high heat conduction and low thermal expansion coefficient and a preparation method thereof, and solves the problems of low heat conductivity and high thermal expansion coefficient of the existing polyimide.
In order to achieve the above object, the present invention provides the following technical solutions:
The polyimide film with high heat conduction and low thermal expansion coefficient comprises the following components in parts by weight: 5-40 parts of organic amine modified heat conducting filler, 50-120 parts of polar solvent, 2-10 parts of dianhydride and 2-12 parts of diamine.
Further, the organic amine is one or more of triethylamine, butylamine, isopropylamine, triethanolamine and ethylenediamine.
Further, the heat conducting filler is a micro-nano three-dimensional netlike SiC whisker-SiC nanowire.
Further, the preparation method of the heat conducting filler comprises the following steps: the preparation method comprises the steps of firstly preparing a SiC whisker preform by a sol-gel method, uniformly mixing 4-35 parts by weight of SiC whisker, 20-30 parts by weight of a silicon solution and 20-30 parts by weight of sodium dodecyl sulfate, adding 1-2.5 parts by weight of ammonium persulfate, uniformly stirring, performing gel reaction to generate a blank, heating at 400-500 ℃ for 2h in an air environment to remove glue to obtain the SiC whisker preform, then dipping 1.5-5 mol/L of catalyst solution on the SiC whisker preform, then at 1000 ℃ taking polycarbosilane as a precursor, taking argon as a carrier, and performing in-situ growth of SiC nanowire on the SiC whisker preform by a chemical vapor deposition method for 30-180 min to obtain the micro-nano three-dimensional network SiC whisker-SiC nanowire heat-conducting filler.
Further, the catalyst is one or a mixture of more of ferric chloride, ferric nitrate and ferric sulfate.
Further, the diameter of the SiC whisker is 1.5-5 mu m, the length of the SiC whisker is 15-30 mu m, the diameter of the SiC nanowire is 20-60 nm, the length of the SiC nanowire is 600-5000 nm, and the mass ratio of the SiC whisker to the SiC nanowire is (5-20): 1.
Further, the preparation method of the organic amine modified heat conducting filler comprises the following steps: under the water bath condition of 50-80 ℃, 5-40 parts of heat conducting filler is added into 4-20 parts of organic amine in parts by weight, the mixture is added into 40-80 parts of ethanol solvent, the mixture is stirred for 2-4 hours, the mixture is filtered and washed by ethanol, and the mixture is dried for 2-4 hours at 50-80 ℃ to obtain the organic amine modified heat conducting filler.
Further, the polar solvent is one or more of dimethylformamide and dimethylacetamide.
Further, the dianhydride is one or more of 3,3', 4' -biphenyl tetracarboxylic dianhydride and 2,2', 3' -biphenyl tetracarboxylic dianhydride.
Further, the diamine is one or more of 2, 6-dimethyl p-phenylenediamine, 2,3, 5-trimethyl p-phenylenediamine and 2, 5-di-tert-butyl p-phenylenediamine.
The invention also provides a preparation method of the polyimide film with high heat conduction and low thermal expansion coefficient, which comprises the following steps:
S1, preparing an organic amine modified heat conduction filler: firstly, uniformly mixing 4-35 parts of SiC whisker, 20-30 parts of silicon solution and 20-30 parts of sodium dodecyl sulfonate according to a weight ratio, then adding 1-2.5 parts of ammonium sulfate, uniformly stirring to enable the solution to undergo a gel reaction to form a green body, and heating the green body in an air environment at 400-500 ℃ for 2 hours to remove colloid components, so as to obtain a SiC whisker preform. Then, a catalyst solution of 1.5-5 mol/L is immersed on the SiC whisker preform, polycarbosilane is used as a precursor, argon is used as a carrier, the growth time is 30-180 min, and in-situ growth of SiC nanowires on the preform is realized, so that the three-dimensional netlike SiC whisker-SiC nanowire heat-conducting filler is obtained. And finally, adding 5-40 parts of heat conducting filler into 4-20 parts of organic amine in parts by weight under the water bath condition of 50-80 ℃, adding into 40-80 parts of ethanol solvent, stirring for 2-4 hours, filtering, washing with ethanol, and drying for 2-4 hours at 50-80 ℃ to obtain the organic amine modified heat conducting filler.
S2, preparing a polyamide acid PAA solution: 2-10 parts of dianhydride and 2-12 parts of diamine are placed in 50-120 parts of polar solvent, the stirring speed is 50-100 r/min, the polycondensation reaction is carried out under the protection of nitrogen, the temperature is 30-50 ℃, and the reaction time is 30-60 minutes.
S3, preparing a polyimide film: adding the organic amine modified heat-conducting filler obtained in the step S1 into the polyamide PAA solution obtained in the step S2, stirring for 4-6 hours, carrying out defoaming treatment by using ultrasonic waves 30 min, conveying the uniformly mixed solution into a casting machine for casting treatment after defoaming, and carrying out heat preservation on the film subjected to casting treatment in a vacuum drying box at each temperature point of 100 ℃ and 150 ℃ for 2 hours for curing treatment, thereby finally obtaining the polyimide film with high heat conduction and low thermal expansion coefficient.
The invention has at least the following beneficial effects:
Firstly, the heat conducting filler selected by the invention is mainly based on the high heat conducting property and the low thermal expansion coefficient of the micro-nano three-dimensional network SiC whisker-SiC nanowire, the heat conducting efficiency of the polyimide film can be effectively improved on the heat conducting property, the low thermal expansion coefficient is helpful for reducing the thermal expansion coefficient of the film, the heat expansion matching property is improved, the heat conducting property and the heat stability of the film are helpful for optimizing, and the requirements of various application scenes are met.
Secondly, the micro-nano three-dimensional netlike SiC whisker-SiC nanowire is introduced into the polyimide film in structural design, so that the multi-scale combination of the micro-nano silicon carbide is realized, the design increases the distribution of the heat conducting filler in a three-dimensional space, avoids the aggregation of the nanowire and forms a three-dimensional heat conducting channel, in addition, the SiC whisker and the SiC nanowire are in an in-situ growth relationship, the bonding strength of the SiC whisker and the SiC nanowire is improved, the heat conducting performance is improved, the contact area between the SiC whisker and the SiC nanowire with high length-diameter ratio and polyimide can be increased at the other part, and the thermal expansion coefficient of polyimide is further reduced. Through optimizing the preparation conditions, the sizes and the distribution of the whiskers and the nanowires can be finely regulated and controlled, and the heat conduction performance and the thermal expansion coefficient of the film are further optimized.
In addition, the surfaces of the SiC whisker and the SiC nanowire modified by the organic amine contain amino groups, and the amino groups react with polyimide to form amide bonds, so that the interface binding force and compatibility of the filler and a polyimide matrix are improved. The method is favorable for further improving the exertion of the heat conducting property of the heat conducting filler in the polyimide film, reducing the heat resistance between the filler and the matrix, and simultaneously, the strong interface combination can also reduce the thermal expansion coefficient so as to meet the specific application requirements, so that the modification step provides powerful support for optimizing the comprehensive performance of the film.
Drawings
FIG. 1 is a SEM micrograph of three-dimensional network SiC whisker-SiC nanowire according to example 1 of the present invention;
FIG. 2 is a SEM microstructure photograph of three-dimensional network SiC whisker-SiC nanowire modified by organic amine in example 1 of the invention;
Fig. 3 is an SEM microstructure photograph of the polyimide film prepared in example 1 of the present invention.
FIG. 4 is a SEM micrograph of three-dimensional network of SiC whiskers-SiC nanowires of example 5 of the invention.
Fig. 5 is an SEM microstructure photograph of the polyimide film prepared in comparative example 1 of the present invention.
In order to make the objects, technical solutions and advantages of the embodiments of the present invention more clear, the technical solutions of the embodiments of the present invention will be clearly and completely described below with reference to the accompanying drawings in the embodiments of the present invention.
Example 1
A polyimide film with high heat conduction and low thermal expansion coefficient comprises the following components in parts by weight: 6 parts of organic amine modified heat conducting filler, 50 parts of polar solvent, 3 parts of dianhydride and 3 parts of diamine.
The organic amine is triethylamine, and the heat conducting filler is micro-nano three-dimensional netty SiC whisker-SiC nanowire.
The preparation method of the heat-conducting filler comprises the following steps: firstly preparing a SiC whisker preform by a sol-gel method, uniformly mixing 5.5 parts of SiC whisker, 20 parts of silicon solution and 20 parts of sodium dodecyl sulfonate by weight, then adding 1.5 parts of ammonium sulfate and uniformly stirring to enable the solution to undergo a gel reaction to form a blank, and heating the blank in an air environment at 450 ℃ for 2 hours to remove colloid components to obtain the SiC whisker preform. Then, 1.5 mol/L of catalyst solution is immersed on the SiC whisker preform, then polycarbosilane is used as a precursor, argon is used as a carrier, the growth time is 60 min, and in-situ growth of SiC nanowires on the preform is realized, so that the three-dimensional netlike SiC whisker-SiC nanowire heat conduction filler is obtained.
The catalyst is ferric chloride.
The diameter of the SiC whisker is 2 mu m, the length of the SiC whisker is 30 mu m, the diameter of the SiC nanowire is 40 nm, the length of the SiC nanowire is 1500 nm, the mass ratio of the SiC whisker to the SiC nanowire is 11:1, and the relationship between the SiC whisker and the SiC nanowire is in-situ growth relationship.
The preparation method of the organic amine modified heat-conducting filler comprises the following steps: under the water bath condition of 50 ℃,6 parts of heat conducting filler is added into 10 parts of organic amine in parts by weight, the mixture is added into 50 parts of ethanol solvent, the mixture is stirred for 3 hours, and after filtration, the mixture is washed by ethanol and dried for 3 hours at 60 ℃ to obtain the organic amine modified heat conducting filler.
The dianhydride is 3,3', 4' -biphenyl tetracarboxylic dianhydride.
The diamine is 2, 5-di-tert-butyl p-phenylenediamine.
The preparation method of the polyimide film with high heat conduction and low thermal expansion coefficient comprises the following steps: firstly, uniformly mixing 5.5 parts of SiC whisker, 20 parts of silicon solution and 20 parts of sodium dodecyl sulfonate according to the weight ratio, then adding 1.5 parts of ammonium sulfate, uniformly stirring to enable the solution to undergo a gel reaction to form a green body, and heating the green body in an air environment at 450 ℃ for 2 hours to remove colloid components to obtain the SiC whisker preform. Then, 1.5 mol/L of catalyst solution is immersed on the SiC whisker preform, then polycarbosilane is used as a precursor, argon is used as a carrier, the growth time is 60min, and in-situ growth of SiC nanowires on the preform is realized, so that the three-dimensional netlike SiC whisker-SiC nanowire heat conduction filler is obtained. Finally, adding 6 parts of heat conducting filler into 10 parts of organic amine in parts by weight under the water bath condition of 50 ℃, adding the heat conducting filler into 50 parts of ethanol solvent, stirring for 3 hours, filtering, washing with ethanol, drying at 60 ℃ for 3 h to obtain the organic amine modified heat conducting filler, placing 3 parts of dianhydride and 3 parts of diamine into 50 parts of dimethylformamide, stirring at the speed of 60r/min, and carrying out polycondensation under the protection of nitrogen at the temperature of 30 ℃ for 30 minutes. Adding 6 parts of organic amine modified heat conducting filler into polyamide PAA solution, stirring for 5 hours, carrying out defoaming treatment by ultrasonic 30min, conveying the uniformly mixed solution into a casting machine for casting treatment after defoaming, and carrying out curing treatment on the film after casting treatment in a vacuum drying oven at each temperature point of 100 ℃,150 ℃ and 250 ℃ for 2 hours respectively, thus finally obtaining the polyimide film with high heat conduction and low thermal expansion coefficient.
Example 2
A polyimide film with high heat conduction and low thermal expansion coefficient comprises the following components in parts by weight:
20 parts of organic amine modified heat conducting filler, 65 parts of polar solvent, 4 parts of dianhydride and 4 parts of diamine.
The organic amine is butylamine, and the heat conduction filler is micro-nano three-dimensional netlike SiC whisker-SiC nanowire.
The preparation method of the heat-conducting filler comprises the following steps: the preparation method comprises the steps of firstly preparing a SiC whisker preform by a sol-gel method, uniformly mixing 18 parts of SiC whisker, 25 parts of silicon solution and 30 parts of sodium dodecyl sulfonate in parts by weight, adding 2 parts of ammonium persulfate, uniformly stirring, performing gel reaction to generate a blank, heating for 2 hours at 450 ℃ in an air environment to obtain the SiC whisker preform, then soaking 3 mol/L of catalyst solution in the SiC whisker preform, and then growing SiC nanowires on the SiC whisker preform in situ by a chemical vapor deposition method at 1000 ℃ by taking polycarbosilane as a precursor and argon as a carrier, wherein the growth time is 60 min, thereby obtaining the micro-nano three-dimensional netlike SiC whisker-SiC nanowire heat-conducting filler.
The catalyst is ferric nitrate.
The diameter of the SiC whisker is 5 mu m, the length of the SiC whisker is 20 mu m, the diameter of the SiC nanowire is 40 nm mu m, the length of the SiC nanowire is 5000 nm, the mass ratio of the SiC whisker to the SiC nanowire is 9:1, and the relationship between the SiC whisker and the SiC nanowire is in-situ growth relationship.
The preparation method of the organic amine modified heat-conducting filler comprises the following steps: under the water bath condition of 60 ℃, 20 parts of heat conduction filler is added into 10 parts of organic amine in parts by weight, the mixture is added into 67 parts of ethanol solvent, the mixture is stirred for 2.5 hours, and after filtration, the mixture is washed by ethanol and dried for 3.5 hours at 60 ℃, the organic amine modified heat conduction filler is obtained.
The dianhydride is mixed with 2,2', 3' -biphenyl tetracarboxylic dianhydride according to the mass ratio of 1:1.
The diamine is 2, 6-dimethyl p-phenylenediamine and 2,3, 5-trimethyl p-phenylenediamine which are mixed according to the mass ratio of 1:1.
The preparation method of the polyimide film with high heat conduction and low thermal expansion coefficient comprises the following steps: firstly, uniformly mixing 18 parts of SiC whisker, 25 parts of silicon solution and 30 parts of sodium dodecyl sulfonate according to weight proportion, adding 2 parts of ammonium persulfate, uniformly stirring, performing gel reaction to generate a blank, heating at 450 ℃ for 2 hours in an air environment to obtain a SiC whisker preform, then soaking 3 mol/L of catalyst solution on the SiC whisker preform, then in 1000 o ℃ with polycarbosilane as a precursor and argon as a carrier, and performing in-situ growth of SiC nanowire on the SiC whisker preform by a chemical vapor deposition method for 60 min to obtain the micro-nano three-dimensional network SiC whisker-SiC nanowire heat-conducting filler. Then adding 20 parts of heat conducting filler into 10 parts of organic amine in parts by weight under the water bath condition of 60 ℃, adding 67 parts of ethanol solvent, stirring for 2.5 hours, filtering, washing with ethanol, drying at 60 ℃ for 3.5 hours to obtain the organic amine modified heat conducting filler, placing 4 parts of dianhydride and 4 parts of diamine into 65 parts of dimethylformamide, stirring at the speed of 80 r/min, and carrying out polycondensation reaction under the protection of nitrogen at the temperature of 38 ℃ for 50 minutes. Adding 20 parts of organic amine modified heat conducting filler into polyamide PAA solution, stirring for 5 hours, carrying out defoaming treatment by ultrasonic 30min, conveying the uniformly mixed solution into a casting machine for casting treatment after defoaming, and carrying out curing treatment on the film after casting treatment in a vacuum drying oven at each temperature point of 100 ℃, 150 ℃ and 250 ℃ for 2 hours respectively, thus obtaining the polyimide film with high heat conduction and low thermal expansion coefficient.
Example 3
The polyimide film with high heat conduction and low thermal expansion coefficient comprises the following components in parts by weight: 30 parts of organic amine modified heat conducting filler, 80 parts of polar solvent, 6 parts of dianhydride and 6 parts of diamine.
Further, the organic amine is a mixture of butylamine and isopropylamine.
Further, the heat conducting filler is a micro-nano three-dimensional netlike SiC whisker-SiC nanowire.
Further, the preparation method of the heat conducting filler comprises the following steps: the preparation method comprises the steps of firstly preparing a SiC whisker preform by a sol-gel method, uniformly mixing 28 parts of SiC whisker, 25 parts of silicon solution and 26 parts of sodium dodecyl sulfonate in parts by weight, adding 2.5 parts of ammonium persulfate, uniformly stirring, performing gel reaction to generate a blank, heating at 500 ℃ for 2h under an air environment to remove glue to obtain the SiC whisker preform, then impregnating 2.5 mol/L of catalyst solution on the SiC whisker preform, and then at 1000 ℃, taking polycarbosilane as a precursor and argon as a carrier, and performing in-situ growth of SiC nanowire on the SiC whisker preform by a chemical vapor deposition method for 60 min to obtain the micro-nano three-dimensional netlike SiC whisker-SiC nanowire heat-conducting filler.
Further, the catalyst is a mixture of ferric chloride and ferric nitrate.
Further, the diameter of the SiC whisker is 4 mu m, the length is 25 mu m, the diameter of the SiC nanowire is 60 nm, the length is 4500 nm, and the mass ratio of the SiC whisker to the SiC nanowire is 19:1.
Further, the relationship between the SiC whisker and the SiC nanowire is an in-situ growth relationship.
Further, the preparation method of the organic amine modified heat conducting filler comprises the following steps: under the water bath condition of 80 ℃,30 parts of heat conducting filler is added into 20 parts of organic amine in parts by weight, the mixture is added into 80 parts of ethanol solvent, the mixture is stirred for 4 hours, and after filtration, the mixture is washed by ethanol and dried for 4 hours at 80 ℃ to obtain the organic amine modified heat conducting filler.
Further, the dianhydride is 3,3', 4' -biphenyl tetracarboxylic dianhydride and 2,2', 3' -biphenyl tetracarboxylic dianhydride are mixed according to the mass ratio of 1:2.
Further, the diamine is 2,3, 5-trimethyl p-phenylenediamine and 2, 5-di-tert-butyl p-phenylenediamine which are mixed according to the mass ratio of 1:2.
The preparation method of the polyimide film with high heat conduction and low thermal expansion coefficient comprises the following steps: firstly, uniformly mixing 28 parts of SiC whisker, 25 parts of silicon solution and 26 parts of sodium dodecyl sulfonate according to the weight ratio, adding 2.5 parts of ammonium persulfate, uniformly stirring, performing gel reaction to generate a blank, heating at 500 ℃ for 2 hours in an air environment to obtain a SiC whisker preform, then impregnating 2.5 mol/L of catalyst solution on the SiC whisker preform, then performing in-situ growth of SiC nanowire on the SiC whisker preform by a chemical vapor deposition method at 1000 ℃ by taking polycarbosilane as a precursor and argon as a carrier, wherein the growth time is 60 min, and obtaining the micro-nano three-dimensional netlike SiC whisker-SiC nanowire heat-conducting filler. And finally, adding 30 parts of heat conducting filler into 20 parts of organic amine in parts by weight under the water bath condition of 80 ℃, adding into 80 parts of ethanol solvent, stirring for 4 hours, filtering, washing with ethanol, drying at 80 ℃ for 4 hours to obtain the organic amine modified heat conducting filler, placing 6 parts of dianhydride and 6 parts of diamine into 80 parts of dimethylacetamide, stirring at the speed of 70 r/min, and carrying out polycondensation under the protection of nitrogen at the temperature of 50 ℃ for 45 minutes. Adding an organic amine modified heat-conducting filler into a polyamide PAA solution, stirring for 6 hours, carrying out defoaming treatment by ultrasonic waves 30 min, conveying the uniformly mixed solution into a casting machine for casting treatment after the defoaming treatment, and carrying out curing treatment on the film subjected to the casting treatment in a vacuum drying oven at each temperature point of 100 ℃, 150 ℃ and 250 ℃ for 2 hours respectively, thus finally obtaining the polyimide film with high heat conduction and low thermal expansion coefficient.
Example 4
The polyimide film with high heat conduction and low thermal expansion coefficient comprises the following components in parts by weight: 40 parts of organic amine modified heat conducting filler, 120 parts of polar solvent, 8 parts of dianhydride and 8 parts of diamine.
Further, the organic amine is one or more of triethylamine, butylamine, isopropylamine, triethanolamine and ethylenediamine.
Further, the heat conducting filler is a micro-nano three-dimensional netlike SiC whisker-SiC nanowire.
Further, the preparation method of the heat conducting filler comprises the following steps: the preparation method comprises the steps of firstly preparing a SiC whisker preform by a sol-gel method, uniformly mixing 36 parts of SiC whisker, 30 parts of silicon solution and 30 parts of sodium dodecyl sulfonate in parts by weight, adding 2.5 parts of ammonium persulfate, uniformly stirring, performing gel reaction to generate a blank, heating at 500 ℃ for 2h in an air environment to remove glue to obtain the SiC whisker preform, then impregnating the SiC whisker preform with 5 mol/L of catalyst solution, and at 1000 ℃, taking polycarbosilane as a precursor and argon as a carrier, and performing in-situ growth of SiC nanowire on the SiC whisker preform by a chemical vapor deposition method for 180min to obtain the micro-nano three-dimensional netlike SiC whisker-SiC nanowire heat-conducting filler.
Further, the catalyst is one or a mixture of more of ferric chloride, ferric nitrate and ferric sulfate.
Further, the diameter of the SiC whisker is 5 mu m, the length of the SiC whisker is 30 mu m, the diameter of the SiC nanowire is 60 nm, the length of the SiC nanowire is 5000 nm, and the mass ratio of the SiC whisker to the SiC nanowire is 7:1.
Further, the relationship between the SiC whisker and the SiC nanowire is an in-situ growth relationship.
Further, the preparation method of the organic amine modified heat conducting filler comprises the following steps: under the water bath condition of 80 ℃,40 parts of heat conducting filler is added into 20 parts of organic amine in parts by weight, the mixture is added into 75 parts of ethanol solvent, the mixture is stirred for 3 hours, and after filtration, the mixture is washed by ethanol and dried for 4 hours at 76 ℃ to obtain the organic amine modified heat conducting filler.
Further, the dianhydride is 2,2', 3' -biphenyl tetracarboxylic dianhydride.
Further, the 2, 5-di-tert-butyl p-phenylenediamine.
The preparation method of the polyimide film with high heat conduction and low thermal expansion coefficient comprises the following steps: firstly, uniformly mixing 36 parts of SiC whisker, 30 parts of silicon solution and 30 parts of sodium dodecyl sulfonate according to a weight ratio, adding 2.5 parts of ammonium persulfate, uniformly stirring, performing gel reaction to generate a blank, heating at 500 o ℃ for 2 hours in an air environment to obtain a SiC whisker preform, then soaking 5mol/L of catalyst solution in the SiC whisker preform, and then performing in-situ growth of SiC nanowire on the SiC whisker preform by a chemical vapor deposition method at 1000 ℃ by taking polycarbosilane as a precursor and argon as a carrier, wherein the growth time is 180 min, thereby obtaining the micro-nano three-dimensional netlike SiC whisker-SiC nanowire heat-conducting filler. And finally, adding 40 parts of heat conducting filler into 20 parts of organic amine in parts by weight under the water bath condition of 80 ℃, adding into 75 parts of ethanol solvent, stirring for 3 hours, filtering, washing with ethanol, and drying at 76 ℃ for 4 hours to obtain the organic amine modified heat conducting filler. 8 parts of dianhydride and 8 parts of diamine are placed in 120 parts of dimethylacetamide, the stirring speed is 100 r/min, and the polycondensation reaction is carried out under the protection of nitrogen, the temperature is 50 ℃, and the reaction time is 60 minutes. Adding an organic amine modified heat-conducting filler into a polyamide PAA solution, stirring for 6 hours, carrying out defoaming treatment by ultrasonic waves 30min, conveying the uniformly mixed solution into a casting machine for casting treatment after the defoaming treatment, and carrying out curing treatment on the film subjected to the casting treatment in a vacuum drying oven at each temperature point of 100 ℃, 150 ℃ and 250 ℃ for 2 hours respectively, thus finally obtaining the polyimide film with high heat conduction and low thermal expansion coefficient.
Example 5
Substantially the same as in example 1, except that the time for growing SiC nanowires was increased from 60 min to 120 min of example 1, otherwise unchanged.
Example 6
Substantially the same as in example 1, except that the component of SiC whiskers was increased from 5.5 parts to 10 parts of example 1, the others were unchanged.
Example 7
Substantially the same as in example 1, except that the organic amine was increased from 10 parts to 15 parts of example 1, the others were unchanged.
Comparative example 1
Substantially the same as in example 1, except that the SiC nanowire was not grown by chemical vapor deposition.
Comparative example 2
Substantially the same as in example 1, except that SiC whiskers were not employed, but an equal amount of SiC nanowires was directly added as a heat conductive filler.
Comparative example 3
Substantially the same as in example 1, except that the heat conductive coating was modified without using an organic amine.
The thermal conductivities, thermal expansion coefficients, and tensile strengths of examples 1 to 7, comparative examples 1 to 3, and conventional commercial polyimide films are shown in table 1, respectively.
The test methods of thermal conductivity and thermal expansion coefficient refer to ASTM ≡d696 standard, and the test methods of tensile strength refer to ASTM ≡d882.
TABLE 1
Compared with the embodiment 1, the embodiments 2-4 increase the contents of the SiC whisker and the SiC nanowire serving as the heat conducting fillers, can increase the heat conducting property and the mechanical property of the polyimide film, and reduce the thermal expansion coefficient.
Compared with the embodiment 1, the thermal conductivity of the SiC nanowire heat conduction filler is reduced from 1.1W/(m.K) to 0.89W/(m.K), the thermal expansion coefficient is increased from 16 ppm/K to 27.3ppm/K, and the tensile strength is reduced from 320 MPa to 230 MPa, so that the SiC nanowire can improve the mechanical property by improving the thermal conductivity of the polyimide, reducing the thermal expansion coefficient.
Compared with the example 1, the thermal conductivity of the comparative example 2 is reduced from 1.1W/(m.K) to 0.79W/(m.K), the thermal expansion coefficient is increased from 16 ppm/K to 24.9ppm/K, and the tensile strength is reduced from 320 MPa to 253 MPa, so that the SiC whisker can improve the mechanical property when improving the thermal conductivity of the polyimide, reducing the thermal expansion coefficient.
Comparative example 3 compared to example 1, without the organic amine modified thermally conductive filler, the thermal conductivity was reduced from 1.1W/(m.K) to 0.63W/(m.K), the thermal expansion coefficient was increased from 16 ppm/K to 28.9ppm/K, and the tensile strength was reduced from 320 MPa to 267 MPa, demonstrating that organic amine modification can increase the interfacial bond of SiC and polyimide to improve mechanical and thermal conductivity, and reduce the thermal expansion coefficient.
FIG. 1 is a photograph of an SEM microstructure of a three-dimensional network SiC whisker-SiC nanowire in example 1 of the invention, and it can be seen that the SiC nanowire grown in situ is uniformly dispersed on the surface of the SiC whisker;
FIG. 2 is a SEM microstructure photograph of an organic amine modified three-dimensional network SiC whisker-SiC nanowire in example 1 of the invention, and the surface of the modified SiC whisker-SiC nanowire can be seen to have obvious modified particles;
fig. 3 is an SEM microstructure photograph of the polyimide film prepared in example 1 of the present invention, and it can be seen that the SiC whisker-SiC nanowire heat conductive filler is dispersed inside the matrix.
Fig. 4 is a photograph of SEM microstructure of three-dimensional network SiC whisker-SiC nanowires in example 5 of the present invention, and it can be clearly seen that the length of SiC nanowire filler increases with the extension of deposition time.
Fig. 5 is a SEM microstructure photograph of the polyimide film prepared in comparative example 1 of the present invention, and it can be clearly seen that there is no SiC nanowire filler.
Finally, it should be noted that: the above embodiments are only for illustrating the technical aspects of the present invention and not for limiting the same, and although the present invention has been described in detail with reference to the above embodiments, it should be understood by those of ordinary skill in the art that: all changes in the structure and details of the invention which may be made in the invention are encompassed by the scope of the invention as defined by the claims.

Claims (4)

1. A polyimide film with high heat conduction and low thermal expansion coefficient comprises the following components in parts by weight:
5-40 parts of organic amine modified heat conducting filler, 50-120 parts of polar solvent, 2-10 parts of dianhydride and 2-12 parts of diamine;
the dianhydride is one or more of 3,3', 4' -biphenyl tetracarboxylic dianhydride and 2,2', 3' -biphenyl tetracarboxylic dianhydride;
The diamine is one or more of 2, 6-dimethyl p-phenylenediamine, 2,3, 5-trimethyl p-phenylenediamine and 2, 5-di-tert-butyl p-phenylenediamine;
The organic amine is one or more of triethylamine, butylamine and isopropylamine;
The heat conducting filler is a micro-nano three-dimensional netlike SiC whisker-SiC nanowire;
The preparation method of the heat conduction filler comprises the following steps: firstly preparing a SiC whisker preform by a sol-gel method, uniformly mixing 4-35 parts by weight of SiC whisker, 20-30 parts by weight of a silicon solution and 20-30 parts by weight of sodium dodecyl sulfate, adding 1-2.5 parts by weight of ammonium persulfate, uniformly stirring, performing gel reaction to generate a blank, heating at 400-500 ℃ for 2h under an air environment to obtain the SiC whisker preform, soaking the SiC whisker preform with 1.5-5 mol/L of a catalyst solution at 1000 ℃, taking polycarbosilane as a precursor, taking argon as a carrier, and performing in-situ growth of SiC nanowire on the SiC whisker preform by a chemical vapor deposition method for 30-180 min to obtain a micro-nano three-dimensional network SiC whisker-SiC nanowire heat conducting filler, wherein the catalyst is one or more of ferric chloride, ferric nitrate and ferric sulfate;
the diameter of the SiC whisker is 1.5-5 mu m, the length of the SiC whisker is 15-30 mu m, the diameter of the SiC nanowire is 20-60 nm, the length of the SiC nanowire is 600-5000 nm, and the mass ratio of the SiC whisker to the SiC nanowire is (5-20): 1.
2. The polyimide film with high heat conduction and low thermal expansion coefficient according to claim 1, wherein the preparation method of the organic amine modified heat conduction filler is as follows:
and adding 5-40 parts of heat conducting filler into 4-20 parts of organic amine in parts by weight under the water bath condition of 50-80 ℃, adding into 40-80 parts of ethanol solvent, stirring for 2-4 hours, filtering, washing with ethanol, and drying at 50-80 ℃ for 2-4 hours to obtain the organic amine modified heat conducting filler.
3. The polyimide film having both high thermal conductivity and low thermal expansion coefficient according to claim 1, wherein said polar solvent is one or more of dimethylformamide and dimethylacetamide.
4. The method for preparing the polyimide film with both high heat conduction and low thermal expansion coefficient according to claim 1, comprising the following steps: firstly, placing 2-10 parts of dianhydride and 2-12 parts of diamine into 50-120 parts of polar solvent, stirring at the speed of 50-100 r/min, carrying out polycondensation reaction under the protection of nitrogen at the temperature of 30-50 ℃ for 30-60 minutes, then adding 5-40 parts of organic amine modified heat conducting filler, stirring for 4-6 hours, carrying out defoaming treatment by ultrasonic 30 min, conveying the uniformly mixed solution into a casting machine for casting treatment after the defoaming, carrying out curing treatment on the film after the casting treatment in a vacuum drying oven at each temperature point of 100 ℃ and 150 ℃ for 2 hours, and finally, demolding to obtain the polyimide film with high heat conduction and low thermal expansion coefficient.
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CN105085914A (en) * 2015-08-25 2015-11-25 中节能万润股份有限公司 High-temperature-resistant polyimide and preparation method thereof
CN109153834A (en) * 2016-05-20 2019-01-04 沙特基础工业全球技术有限公司 Composite material including fluoroelastomer and polyimides prepares the method for composite material and the product comprising it
CN110776657A (en) * 2019-11-05 2020-02-11 株洲时代新材料科技股份有限公司 High-thermal-conductivity polyimide film and preparation method thereof
CN111793206A (en) * 2020-06-09 2020-10-20 中天电子材料有限公司 Preparation method of polyimide film and polyimide film

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105085914A (en) * 2015-08-25 2015-11-25 中节能万润股份有限公司 High-temperature-resistant polyimide and preparation method thereof
CN109153834A (en) * 2016-05-20 2019-01-04 沙特基础工业全球技术有限公司 Composite material including fluoroelastomer and polyimides prepares the method for composite material and the product comprising it
CN110776657A (en) * 2019-11-05 2020-02-11 株洲时代新材料科技股份有限公司 High-thermal-conductivity polyimide film and preparation method thereof
CN111793206A (en) * 2020-06-09 2020-10-20 中天电子材料有限公司 Preparation method of polyimide film and polyimide film

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