CN109401313B - Polyimide film and preparation method thereof - Google Patents
Polyimide film and preparation method thereof Download PDFInfo
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Abstract
The invention provides a polyimide film, which is prepared by tape casting and imidization stretching of a polyamic acid solution composition, wherein the polyamic acid solution composition is mainly prepared by mixing the following components in parts by weight: 100-150 parts of polyamide acid resin, 5-20 parts of plasticizer, 0.5-10 parts of slipping agent and 50-125 parts of heat-conducting slurry. The polyimide film prepared by the invention has high heat-conducting property and excellent mechanical property, is easy to process and mold, realizes industrial production, and has wide application prospect in the aspect of interface heat-conducting insulating materials. The invention also provides a preparation method of the polyimide film, and the preparation method has the advantages of short process flow, simple operation, low cost, environmental friendliness and suitability for large-scale production.
Description
Technical Field
The invention belongs to the field of polymer composite materials, and particularly relates to a polyimide film and a preparation method thereof.
Background
Polyimide (PI) films have excellent thermal stability, electrical insulation, mechanical properties, and dielectric properties, and are widely used in the fields of microelectronic integrated circuits, flexible printed circuit substrates, rail transit, aerospace, and the like. However, the conventional polyimide film has a thermal conductivity of only about 0.16W/(m · K), has poor thermal conductivity, and is easily overheated when applied to high-density and high-speed operation of microelectronic devices, thereby affecting the stability of devices and integrated circuits.
At present, in the research and development of a high-thermal-conductivity polyimide film, inorganic thermal-conductivity fillers such as aluminum oxide, beryllium oxide, magnesium oxide, aluminum nitride, boron nitride, graphite powder and the like are mainly filled in a polymer to form a thermal-conductivity network in a composite material, so that the thermal conductivity of the material is improved. When the amount of the inorganic heat-conducting filler dispersed in the resin is small, the filler is uniformly dispersed in the resin, but the filler cannot be mutually contacted and interacted, so that the heat-conducting property is not greatly improved; when the amount of the filler is large, on one hand, the inorganic heat-conducting filler prevents the movement of molecular chains in the polymer, so that the toughness of the matrix is reduced, and on the other hand, the crack between the inorganic heat-conducting filler and the matrix is expanded under the action of an external load, so that the material is broken and fails. Therefore, although the heat conductivity of the film can be greatly improved by filling a large amount of inorganic heat-conducting filler, the comprehensive performance of the film, especially the mechanical properties such as toughness and the like, is remarkably reduced, so that the polyimide film is easy to crack and even cannot be cast and stretched to form a film, and the problem in practical application is large. Many researchers introduce a large amount of flexible groups such as ether bond into the polyimide molecular chain in order to improve the toughness of the film, but at the same time, the adhesive property between the film and the casting matrix is increased, so that the film cannot be peeled from the matrix, and therefore, the industrial production is difficult to realize.
Disclosure of Invention
The technical problem to be solved by the present invention is to overcome the above mentioned disadvantages and drawbacks in the background art, and to provide a polyimide film with excellent thermal conductivity and mechanical properties, and to provide a method for preparing the polyimide film, which is easy to implement industrial production.
In order to solve the technical problems, the technical scheme provided by the invention is as follows:
the polyimide film is prepared by casting, imidizing and stretching a polyamic acid solution composition, and in order to improve the comprehensive performance of the film, the polyamic acid solution composition is mainly prepared by mixing the following components in parts by weight:
100-150 parts of polyamide acid resin,
5-20 parts of plasticizer,
0.5-10 parts of slipping agent,
50-125 parts of heat-conducting slurry.
In the polyimide film, the plasticizer is preferably an aliphatic dibasic acid ester and/or an amide compound having two or more amide bonds.
In the polyimide film, the aliphatic dibasic acid ester is preferably at least one of dimethyl phthalate, diethyl phthalate, dibutyl phthalate, sulfonamides, triphenyl phosphate, diallyl phthalate, dioctyl phthalate, diisooctyl phthalate, dioctyl sebacate, dioctyl oxalate, dibutyl sebacate, butyl epoxy fatty acid ester, octyl epoxy fatty acid ester, trioctyl trimellitate, chlorohydrocarbon-50, phenyl petroleum sulfonate, chlorinated petroleum ester, and dipentaerythritol ester.
According to the polyimide film, the first type of micromolecule plasticizer is selected, so that on one hand, the distance between high molecular chains can be effectively increased, the friction force of interaction between the high molecular chain sections and between the high molecular chains and the inorganic heat-conducting filler is weakened, the mobility of the polymer molecular chains is increased, and the chain section movement is realized; on the other hand, the insertion of a proper amount of small-molecule plasticizer plays a certain role in diluting the mixed solution of the polyamic acid and the inorganic heat-conducting filler, so that the wettability of the polyamic acid on the surface of the inorganic heat-conducting filler is enhanced, the number of microcracks between the polyimide matrix and the inorganic heat-conducting filler is effectively reduced, and the crystallinity of a polymer molecular chain is reduced, thereby realizing that the mechanical property of the composite material is improved while the heat-conducting property is greatly promoted by doping the high-content filler.
In the polyimide film, the molecular weight of the amide-based compound having two or more amide bonds is preferably 100 to 3000. In order to improve the compatibility of the plasticizer and the reaction system, promote the uniform dispersion of the plasticizer in the reaction system and ensure good plasticizing effect, the molecular weight of the second type of plasticizer needs to be controlled within the range of the invention.
According to the polyimide film, the selected second type of micromolecule plasticizer is inserted between the inorganic heat-conducting filler and the polyimide matrix by utilizing the synthesized micromolecules, and a hydrogen bond is formed between an amido bond of the micromolecule plasticizer and a polyimide molecular chain, so that the inorganic heat-conducting filler is pinned, and the expansion of microcracks between the inorganic heat-conducting filler and the polyimide matrix under the action of external load is further prevented; meanwhile, the synthesized small molecular plasticizer also plays a certain role in diluting the polyamic acid, enhances the wettability of the polyamic acid on the surface of the inorganic heat-conducting filler, and effectively reduces the number of microcracks between the polyimide matrix and the inorganic heat-conducting filler. The number of the microcracks is reduced, and simultaneously, the hydrogen bonds play a stronger role in hindering the expansion of the microcracks, so that the comprehensive mechanical property of the polyimide heat-conducting composite film doped with the high-content inorganic heat-conducting filler is greatly improved.
The synthetic route of the second plasticizer selected by the invention is as follows:
reacting micromolecules containing more than two amino groups with acetyl chloride according to a certain proportion to synthesize micromolecules or low molecular weight compounds with more than two amido bonds.
For example, a small molecule with two amino groups and acetyl chloride are synthesized into a small molecule with two amide groups according to the ratio of 1:2, and the structural general formula of the small molecule is shown as the formula (1):
wherein R1, R2 and R3 are alkyl groups or groups having a benzene ring.
Similarly, a small molecule with three amido groups and acetyl chloride are synthesized into a small molecule with three amido bonds according to the ratio of 1:3, and the structural general formula is shown as the formula (2):
r1, R2, R3, R4, R5 and R6 are alkyl groups or groups having a benzene ring.
The specific example is that micromolecule melamine with three amino groups and acetyl chloride react according to a ratio of 1:3 to synthesize micromolecule with three amido bonds, and the structural general formula is shown as formula (3):
in the polyimide film, the slipping agent is preferably at least one of oleamide, erucamide and octadecanamide. By adding the slipping agent, the extensibility of the composite film is increased, the tear strength of the composite film is improved, and the friction coefficient and the bonding resistance of the PAA resin are reduced, so that the bonding and the agglomeration of the inorganic heat-conducting filler in the flow film process are effectively prevented. The slipping agent migrates to the surface of the polyimide film after tape casting and heating to form a lubricating layer, so that the polyimide film is easier to peel and process and form, and the phenomenon of adhering a tape casting matrix is not easy to occur even if flexible groups and the like are introduced into the polyimide.
Preferably, the heat-conducting paste comprises the following components in parts by weight:
10-50 parts of inorganic heat-conducting filler,
0.5-10 parts of surfactant,
0.5-10 parts of anti-settling agent,
50-90 parts of a polar solvent.
In the polyimide film, preferably, the inorganic heat-conducting filler is at least one of aluminum nitride, boron nitride and aluminum oxide, and the particle size of the inorganic heat-conducting filler is 100nm to 5000 nm;
the surfactant is 4-aminopropyl methyl dimethoxy silane, 3-aminopropyl methyl diethoxy silane, 3-aminopropyl trimethoxy silane, 3-aminopropyl triethoxy silane, N-2-aminoethyl-3-aminopropyl methyl diethoxy silane, N- (2-aminoethyl) -3-aminopropyl methyl dimethoxy silane, at least one of N-2-aminoethyl-3-aminopropyltriethoxysilane, N-2-aminoethyl-3-aminopropyltrimethoxysilane, N- (piperazinylethyl) -3-aminopropylmethyldimethoxysilane, 3-divinyltriaminopropylmethyldimethoxysilane and 3-divinyltriaminopropyltrimethoxysilane; according to the polyimide film, the surfactant acts with the inorganic heat-conducting filler through physical coating or chemical grafting, so that the interaction force among particles is reduced, and the binding force between the particles and a matrix is enhanced.
The anti-settling agent is N-methyl pyrrolidone solution of polyamide wax and/or modified urea. The polyimide film has the advantages that the particle size of the heat-conducting slurry is larger, the gravity settling effect is obvious, the anti-settling agent is added to be dispersed and activated in the system, long chains of the swollen anti-settling agent are mutually wound to form a thixotropic structure, and the dispersed inorganic heat-conducting filler slurry can be prevented from settling under the action of gravity.
Preferably, the polyamic acid resin comprises the following components in parts by weight:
10-20 parts of polyamide acid,
40-180 parts of a polar solvent;
the polyamic acid is prepared by performing polycondensation reaction on diamine and dianhydride in equal molar ratio in a polar solvent;
the dianhydride is at least one of pyromellitic dianhydride, 3,3',4,4' -biphenyltetracarboxylic dianhydride, 2,3,3',4' -diphenyl ether tetracarboxylic dianhydride, 3,3',4,4' -benzophenone tetracarboxylic dianhydride, bisphenol A type diether dianhydride, 2 '-bis [4- (3, 4-dicarboxyphenoxy) phenyl ] propane tetracarboxylic dianhydride and 2,2' -bis (3, 4-dicarboxyphenyl) hexafluoropropane tetracarboxylic dianhydride;
the diamine is at least one of 4,4' -diaminodiphenyl ether, 3,4' -diaminodiphenyl ether, p-phenylenediamine, o-phenylenediamine, m-phenylenediamine and 2,2' -bis [ (4-aminophenoxy) phenyl ] propane.
In the polyimide film, the polar solvent is preferably at least one of N-methylpyrrolidone, N-dimethylformamide, and N, N-dimethylacetamide.
As a general inventive concept, the present invention also provides a method for preparing the polyimide film, including the steps of:
defoaming polyamide acid resin, uniformly mixing with heat-conducting slurry, plasticizer and slipping agent to obtain polyamide acid solution composition, casting onto a steel belt, keeping the temperature of 100-120 ℃ for 10-20 min, keeping the temperature of 140-160 ℃ for 10-20 min, keeping the temperature of 180-220 ℃ for 10-20 min, keeping the temperature of 220-280 ℃ for 10-20 min, and keeping the temperature of 320-380 ℃ for 10-20 min, and performing stretching imidization to obtain the polyimide film. The parameters of the imidization process are controlled within the range of the invention, which is beneficial to improving the comprehensive performance of the composite film.
In the above preparation method, preferably, the preparation method of the polyamic acid resin includes the specific operation steps of: under the atmosphere of nitrogen, adding diamine and dianhydride in equal molar ratio into a polar solvent, and stirring for 4-6 hours at the temperature of-20-30 ℃ to obtain polyamide acid resin;
the preparation method of the heat-conducting slurry comprises the following specific operation steps: dispersing the inorganic heat-conducting filler, the surfactant, the anti-settling agent and the polar solvent uniformly by a high-speed dispersion machine, and then putting the mixture into a sand mill for grinding and modification to obtain the heat-conducting slurry.
Compared with the prior art, the invention has the advantages that:
according to the invention, the micromolecule plasticizer is inserted between the polyamic acid molecular chains, so that the attraction between the polymer molecular chains is weakened, the mobility of the polyamic acid molecular chains is increased, the number of microcracks between the inorganic heat-conducting filler and the polyimide substrate is effectively reduced, the expansion of the microcracks under the action of an external load is prevented, the toughness of the polyimide film is increased, and the problem that the film is difficult to process and form due to the high-content inorganic heat-conducting filler is solved.
The invention also adds the slipping agent, increases the extensibility of the composite film, improves the tear strength of the composite film, and reduces the friction coefficient and the bonding resistance of the PAA resin, thereby effectively preventing the bonding and the agglomeration of the inorganic heat-conducting filler in the process of flowing the film and leading the polyimide film to be easier to peel and process and form.
The invention also adds the surfactant and the anti-settling agent into the heat-conducting slurry, thereby reducing the interaction force among the filler particles, enhancing the binding force between the filler particles and the matrix, and simultaneously preventing the dispersed inorganic heat-conducting filler slurry from settling under the action of gravity, thereby further improving the heat-conducting property and the mechanical property of the polyimide film.
In general, the polyimide film prepared by the invention has high heat conductivity and excellent mechanical property, is easy to machine and form, realizes industrial production, and has wide application prospect in the aspect of interface heat-conducting insulating materials. The method for preparing the polyimide film has the advantages of short process flow, simple operation, low cost and environmental friendliness, and is suitable for large-scale 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:
the polyimide film is prepared by casting, imidizing and stretching a polyamic acid solution composition, wherein the polyamic acid solution composition is mainly prepared by mixing the following components in parts by weight:
178.76g of polyamic acid resin,
10g of dimethyl phthalate,
10g of erucamide,
Thermally conductive paste 124.77 g.
Wherein, the polyamic acid is prepared by sequentially adding 20.02g (0.10mol) of 4,4' -diaminodiphenyl ether and 21.81g (0.10mol) of pyromellitic dianhydride into 136.93g N, N-dimethylformamide for polymerization; the thermal conductive slurry was prepared by mixing 22.51g of alumina having a particle size of 1 μm, 1.13g of 4-aminopropylmethyldimethoxysilane, 1.13g of N-methylpyrrolidone solution of modified urea, and 100g N, N-dimethylformamide.
The preparation method of the polyimide film comprises the following steps:
(1) under the protection of nitrogen atmosphere, sequentially adding 20.02g (0.10mol) of 4,4' -diaminodiphenyl ether and 21.81g (0.10mol) of pyromellitic dianhydride into 136.93g N, N-dimethylformamide, and mechanically stirring at-20-30 ℃ for 3 hours to synthesize polyamide acid resin;
(2) 22.51g of alumina with the particle size of 1 mu m, 1.13g of 4-aminopropylmethyldimethoxysilane and 1.13g of N-methylpyrrolidone solution of modified urea are mixed with 100g N, N-dimethylformamide, treated by a high-speed dispersion machine with the speed of 3000r/min for 2 hours, uniformly dispersed and then put into a sand mill for grinding and modification for 2 hours to prepare heat-conducting slurry;
(3) defoaming the polyamic acid resin, blending the defoamed polyamic acid resin with heat-conducting slurry, 10g of dimethyl phthalate and 10g of erucamide, fully and uniformly mixing the mixture by a screw mixer to obtain a polyamic acid solution composition, casting the polyamic acid solution composition onto a steel belt, keeping the temperature of 120 ℃ for 10min to remove part of solvent, keeping the temperature of 150 ℃ for 10min, keeping the temperature of 200 ℃ for 10min, keeping the temperature of 250 ℃ for 10min, keeping the temperature of 320-380 ℃ for 10min, and stretching and imidizing to obtain the polyimide film.
Example 2:
the polyimide film is prepared by casting, imidizing and stretching a polyamic acid solution composition, wherein the polyamic acid solution composition is mainly prepared by mixing the following components in parts by weight:
240.15g of polyamic acid resin,
10g of dimethyl phthalate,
10g of erucamide,
Thermally conductive paste 130.20 g.
Wherein, the polyamic acid is prepared by sequentially adding 20.02g (0.10mol) of 4,4' -diaminodiphenyl ether and 31.02g (0.10mol) of 2,3',3,4' -diphenyl ether tetracarboxylic dianhydride into 189.11g of N, N-dimethylformamide for polymerization; the thermal conductive slurry was prepared by mixing 27.46g of alumina having a particle size of 1 μm, 1.37g of 4-aminopropylmethyldimethoxysilane, 1.37g of N-methylpyrrolidone solution of modified urea, and 100g N, N-dimethylformamide.
Example 2 compared with example 1, a highly thermally conductive polyimide film was prepared in the same manner as in example 1, with only a change in the kind of dianhydride.
The preparation method of the polyimide film of the embodiment comprises the following steps:
(1) under the protection of nitrogen atmosphere, adding 20.02g (0.10mol) of 4,4' -diaminodiphenyl ether and 31.02g (0.10mol) of 2,3',3,4' -diphenyl ether tetracarboxylic dianhydride into 189.11g of N, N-dimethylformamide in sequence, and mechanically stirring for 3 hours at-20 to 30 ℃ to synthesize polyamide acid resin;
(2) 27.46g of alumina with the particle size of 1 mu m, 1.37g of 4-aminopropylmethyldimethoxysilane and 1.37g of N-methylpyrrolidone solution of modified urea are mixed with 100g N, N-dimethylformamide, treated by a high-speed dispersion machine with the speed of 3000r/min for 2 hours, uniformly dispersed and then put into a sand mill for grinding and modification for 2 hours to prepare heat-conducting slurry;
(3) defoaming the polyamic acid resin, blending the defoamed polyamic acid resin with heat-conducting slurry, 10g of dimethyl phthalate and 10g of erucamide, fully and uniformly mixing the mixture by a screw mixer to obtain a polyamic acid solution composition, casting the polyamic acid solution composition onto a steel belt, keeping the temperature of 120 ℃ for 10min to remove part of solvent, keeping the temperature of 150 ℃ for 10min, keeping the temperature of 200 ℃ for 10min, keeping the temperature of 250 ℃ for 10min, keeping the temperature of 320-380 ℃ for 10min, and stretching and imidizing to obtain the polyimide film.
Example 3:
the polyimide film is prepared by casting, imidizing and stretching a polyamic acid solution composition, wherein the polyamic acid solution composition is mainly prepared by mixing the following components in parts by weight:
178.76g of polyamic acid resin,
15g of dimethyl phthalate,
15g of erucamide,
Thermally conductive paste 124.77 g.
Wherein, the polyamic acid is prepared by sequentially adding 20.02g (0.10mol) of 4,4' -diaminodiphenyl ether and 21.81g (0.10mol) of pyromellitic dianhydride into 136.93g N, N-dimethylformamide for polymerization; the thermal conductive slurry was prepared by mixing 22.51g of alumina having a particle size of 1 μm, 1.13g of 4-aminopropylmethyldimethoxysilane, 1.13g of N-methylpyrrolidone solution of modified urea, and 100g N, N-dimethylformamide.
Example 3 compared with example 1, a highly thermally conductive polyimide film was prepared in the same manner as in example 1, except that the amounts of the plasticizer and the slip agent were changed.
The preparation method of the polyimide film of the embodiment comprises the following steps:
(1) under the protection of nitrogen atmosphere, sequentially adding 20.02g (0.10mol) of 4,4' -diaminodiphenyl ether and 21.81g (0.10mol) of pyromellitic dianhydride into 136.93g N, N-dimethylformamide, and mechanically stirring at-20-30 ℃ for 3 hours to synthesize polyamide acid resin;
(2) 22.51g of alumina with the particle size of 1 mu m, 1.13g of 4-aminopropylmethyldimethoxysilane and 1.13g of N-methylpyrrolidone solution of modified urea are mixed with 100g N, N-dimethylformamide, treated by a high-speed dispersion machine with the speed of 3000r/min for 2 hours, uniformly dispersed and then put into a sand mill for grinding and modification for 2 hours to prepare heat-conducting slurry;
(3) defoaming the polyamic acid resin, blending the defoamed polyamic acid resin with heat-conducting slurry, 15g of dimethyl phthalate and 15g of erucamide, fully and uniformly mixing the mixture by a screw mixer to obtain a polyamic acid solution composition, casting the polyamic acid solution composition onto a steel belt, keeping the temperature of 120 ℃ for 10min to remove part of solvent, keeping the temperature of 150 ℃ for 10min, keeping the temperature of 200 ℃ for 10min, keeping the temperature of 250 ℃ for 10min, keeping the temperature of 320-380 ℃ for 10min, and stretching and imidizing to obtain the polyimide film.
Example 4:
the polyimide film is prepared by casting, imidizing and stretching a polyamic acid solution composition, wherein the polyamic acid solution composition is mainly prepared by mixing the following components in parts by weight:
178.76g of polyamic acid resin,
10g of dimethyl phthalate,
10g of erucamide,
Thermally conductive paste 124.77 g.
Wherein, the polyamic acid is prepared by sequentially adding 20.02g (0.10mol) of 4,4' -diaminodiphenyl ether and 21.81g (0.10mol) of pyromellitic dianhydride into 136.93g N, N-dimethylformamide for polymerization; the thermally conductive slurry was prepared by mixing 22.51g of boron nitride having a particle size of 1 μm, 1.13g of 4-aminopropylmethyldimethoxysilane, 1.13g of N-methylpyrrolidone solution of modified urea, and 100g N, N-dimethylformamide.
Example 4 compared with example 1, a highly thermally conductive polyimide film was prepared in the same manner as in example 1, except that the kind of the inorganic thermally conductive filler was changed.
The preparation method of the polyimide film of the embodiment comprises the following steps:
(1) under the protection of nitrogen atmosphere, sequentially adding 20.02g (0.10mol) of 4,4' -diaminodiphenyl ether and 21.81g (0.10mol) of pyromellitic dianhydride into 136.93g N, N-dimethylformamide, and mechanically stirring at-20-30 ℃ for 3 hours to synthesize polyamide acid resin;
(2) 22.51g of boron nitride with the particle size of 1 mu m, 1.13g of 4-aminopropylmethyldimethoxysilane and 1.13g of N-methylpyrrolidone solution of modified urea are mixed with 100g N, N-dimethylformamide, treated by a high-speed dispersion machine with the speed of 3000r/min for 2 hours, uniformly dispersed and then put into a sand mill for grinding and modification for 2 hours to prepare heat-conducting slurry;
(3) defoaming the polyamic acid resin, blending the defoamed polyamic acid resin with heat-conducting slurry, 10g of dimethyl phthalate and 10g of erucamide, fully and uniformly mixing the mixture by a screw mixer to obtain a polyamic acid solution composition, casting the polyamic acid solution composition onto a steel belt, keeping the temperature of 120 ℃ for 10min to remove part of solvent, keeping the temperature of 150 ℃ for 10min, keeping the temperature of 200 ℃ for 10min, keeping the temperature of 250 ℃ for 10min, keeping the temperature of 320-380 ℃ for 10min, and stretching and imidizing to obtain the polyimide film.
Example 5:
the polyimide film is prepared by casting, imidizing and stretching a polyamic acid solution composition, wherein the polyamic acid solution composition is mainly prepared by mixing the following components in parts by weight:
178.76g of polyamic acid resin,
10g of dioctyl phthalate,
10g of octadecanamide,
Thermally conductive paste 124.77 g.
Wherein, the polyamic acid is prepared by sequentially adding 20.02g (0.10mol) of 4,4' -diaminodiphenyl ether and 21.81g (0.10mol) of pyromellitic dianhydride into 136.93g N, N-dimethylformamide for polymerization; the thermal conductive slurry was prepared by mixing 22.51g of alumina having a particle size of 1 μm, 1.13g of 4-aminopropylmethyldimethoxysilane, 1.13g of N-methylpyrrolidone solution of modified urea, and 100g N, N-dimethylformamide.
Example 5 compared with example 1, the kind of the plasticizer and the slip agent were changed, and the high thermal conductive polyimide film was prepared in the same manner as in example 1.
The preparation method of the polyimide film of the embodiment comprises the following steps:
(1) under the protection of nitrogen atmosphere, sequentially adding 20.02g (0.10mol) of 4,4' -diaminodiphenyl ether and 21.81g (0.10mol) of pyromellitic dianhydride into 136.93g N, N-dimethylformamide, and mechanically stirring at-20-30 ℃ for 3 hours to synthesize polyamide acid resin;
(2) 22.51g of alumina with the particle size of 1 mu m, 1.13g of 4-aminopropylmethyldimethoxysilane and 1.13g of N-methylpyrrolidone solution of modified urea are mixed with 100g N, N-dimethylformamide, treated by a high-speed dispersion machine with the speed of 3000r/min for 2 hours, uniformly dispersed and then put into a sand mill for grinding and modification for 2 hours to prepare heat-conducting slurry;
(3) defoaming the polyamic acid resin, blending the defoamed polyamic acid resin with heat-conducting slurry, 10g of dioctyl phthalate and 10g of octadecanamide, fully and uniformly mixing the mixture by a screw mixer to obtain a polyamic acid solution composition, casting the polyamic acid solution composition onto a steel belt, keeping the temperature of 120 ℃ for 10min to remove part of solvent, keeping the temperature of 150 ℃ for 10min, keeping the temperature of 200 ℃ for 10min, keeping the temperature of 250 ℃ for 10min, keeping the temperature of 320-380 ℃ for 10min, and performing stretch imidization to obtain the polyimide film.
Example 6:
the polyimide film is prepared by casting, imidizing and stretching a polyamic acid solution composition, wherein the polyamic acid solution composition is mainly prepared by mixing the following components in parts by weight:
178.76g of polyamic acid resin,
10g of diamide oligomer,
10g of erucamide,
Thermally conductive paste 124.77 g.
Wherein, the polyamic acid is prepared by sequentially adding 20.02g (0.10mol) of 4,4' -diaminodiphenyl ether and 21.81g (0.10mol) of pyromellitic dianhydride into 136.93g N, N-dimethylformamide for polymerization; the thermal conductive slurry was prepared by mixing 22.51g of alumina having a particle size of 1 μm, 1.13g of 4-aminopropylmethyldimethoxysilane, 1.13g of N-methylpyrrolidone solution of modified urea, and 100g N, N-dimethylformamide.
Example 6 compared with example 1, a high thermal conductive polyimide film was prepared using a small molecular compound having two amide bonds as a plasticizer in the same manner as in example 1.
The preparation method of the polyimide film of the embodiment comprises the following steps:
(1) under the protection of nitrogen atmosphere, sequentially adding 20.02g (0.10mol) of 4,4' -diaminodiphenyl ether and 21.81g (0.10mol) of pyromellitic dianhydride into 136.93g N, N-dimethylformamide, and mechanically stirring at-20-30 ℃ for 3 hours to synthesize polyamide acid resin;
(2) 22.51g of alumina with the particle size of 1 mu m, 1.13g of 4-aminopropylmethyldimethoxysilane and 1.13g of N-methylpyrrolidone solution of modified urea are mixed with 100g N, N-dimethylformamide, treated by a high-speed dispersion machine with the speed of 3000r/min for 2 hours, uniformly dispersed and then put into a sand mill for grinding and modification for 2 hours to prepare heat-conducting slurry;
(3) adding 7.41g (0.10mol) of 1, 2-propane diamine, 16.49g (0.21mol) of acetyl chloride and 10g of triethylamine into 70g of DMF (N, N-dimethylformamide) for reaction, and separating by filtration and reduced pressure distillation after the reaction is finished to obtain a diamide oligomer with two amido bonds;
(4) defoaming the polyamic acid resin, blending the defoamed polyamic acid resin with heat-conducting slurry, 10g of diamide oligomer and 10g of erucamide, fully and uniformly mixing the mixture by a screw mixer to obtain a polyamic acid solution composition, casting the polyamic acid solution composition onto a steel belt, keeping the temperature of 120 ℃ for 10min to remove part of solvent, keeping the temperature of 150 ℃ for 10min, keeping the temperature of 200 ℃ for 10min, keeping the temperature of 250 ℃ for 10min, keeping the temperature of 320-380 ℃ for 10min, and stretching and imidizing to obtain the polyimide film.
Example 7:
the polyimide film is prepared by casting, imidizing and stretching a polyamic acid solution composition, wherein the polyamic acid solution composition is mainly prepared by mixing the following components in parts by weight:
178.76g of polyamic acid resin,
10g of triamide oligomer,
10g of erucamide,
Thermally conductive paste 124.77 g.
Wherein, the polyamic acid is prepared by sequentially adding 20.02g (0.10mol) of 4,4' -diaminodiphenyl ether and 21.81g (0.10mol) of pyromellitic dianhydride into 136.93g N, N-dimethylformamide for polymerization; the thermal conductive slurry was prepared by mixing 22.51g of alumina having a particle size of 1 μm, 1.13g of 4-aminopropylmethyldimethoxysilane, 1.13g of N-methylpyrrolidone solution of modified urea, and 100g N, N-dimethylformamide.
Example 7 compared to example 1, a high thermal conductive polyimide film was prepared using a small molecular compound having three amide bonds as a plasticizer in the same manner as in example 1.
The preparation method of the polyimide film of the embodiment comprises the following steps:
(1) under the protection of nitrogen atmosphere, sequentially adding 20.02g (0.10mol) of 4,4' -diaminodiphenyl ether and 21.81g (0.10mol) of pyromellitic dianhydride into 136.93g N, N-dimethylformamide, and mechanically stirring at-20-30 ℃ for 3 hours to synthesize polyamide acid resin;
(2) 22.51g of alumina with the particle size of 1 mu m, 1.13g of 4-aminopropylmethyldimethoxysilane and 1.13g of N-methylpyrrolidone solution of modified urea are mixed with 100g N, N-dimethylformamide, treated by a high-speed dispersion machine with the speed of 3000r/min for 2 hours, uniformly dispersed and then put into a sand mill for grinding and modification for 2 hours to prepare heat-conducting slurry;
(3) adding 12.61g (0.10mol) of melamine, 24.34g (0.31mol) of acetyl chloride and 15g of triethylamine into 70g of DMF (N, N-dimethylformamide) for reaction at the reaction temperature of 60 ℃, and after the reaction is finished, separating by filtering and reduced pressure distillation to obtain a triamide oligomer with three amido bonds;
(4) defoaming the polyamic acid resin, blending the defoamed polyamic acid resin with heat-conducting slurry, 10g of triamide oligomer and 10g of erucamide, fully and uniformly mixing the mixture by a screw mixer to obtain a polyamic acid solution composition, casting the polyamic acid solution composition onto a steel belt, keeping the temperature of 120 ℃ for 10min to remove part of solvent, keeping the temperature of 150 ℃ for 10min, keeping the temperature of 200 ℃ for 10min, keeping the temperature of 250 ℃ for 10min, keeping the temperature of 320-380 ℃ for 10min, and stretching and imidizing to obtain the polyimide film.
Comparative example 1:
a polyimide film is prepared by casting, imidizing and stretching a polyamic acid solution composition, wherein the polyamic acid solution composition is mainly prepared by mixing the following components in parts by weight:
178.76g of polyamic acid resin,
Thermally conductive paste 124.77 g.
Wherein, the polyamic acid is prepared by sequentially adding 20.02g (0.10mol) of 4,4' -diaminodiphenyl ether and 21.81g (0.10mol) of pyromellitic dianhydride into 136.93g N, N-dimethylformamide for polymerization; the thermal conductive slurry was prepared by mixing 22.51g of alumina having a particle size of 1 μm, 1.13g of 4-aminopropylmethyldimethoxysilane, 1.13g of N-methylpyrrolidone solution of modified urea, and 100g N, N-dimethylformamide.
Comparative example 1 compared to example 1, a highly thermal conductive polyimide film was prepared in the same manner as in example 1, without using a plasticizer and a slip agent.
The preparation method of the polyimide film of the comparative example includes the following steps:
(1) under the protection of nitrogen atmosphere, sequentially adding 20.02g (0.10mol) of 4,4' -diaminodiphenyl ether and 21.81g (0.10mol) of pyromellitic dianhydride into 136.93g N, N-dimethylformamide, and mechanically stirring at-20-30 ℃ for 3 hours to synthesize polyamide acid resin;
(2) 22.51g of alumina with the particle size of 1 mu m, 1.13g of 4-aminopropylmethyldimethoxysilane and 1.13g of N-methylpyrrolidone solution of modified urea are mixed with 100g N, N-dimethylformamide, treated by a high-speed dispersion machine with the speed of 3000r/min for 2 hours, uniformly dispersed and then put into a sand mill for grinding and modification for 2 hours to prepare heat-conducting slurry;
(3) defoaming the polyamic acid resin, blending the polyamic acid resin with the heat-conducting slurry, fully and uniformly mixing the mixture by a screw mixer, casting the mixture onto a steel belt, keeping the temperature at 120 ℃ for 10min to remove part of solvent, keeping the temperature at 150 ℃ for 10min, keeping the temperature at 200 ℃ for 10min, keeping the temperature at 250 ℃ for 10min, keeping the temperature at 320-380 ℃ for 10min, and stretching and imidizing the mixture to obtain the polyimide film.
Comparative example 2:
the polyimide film is prepared by casting, imidizing and stretching a polyamic acid solution composition, wherein the polyamic acid solution composition is mainly prepared by mixing the following components in parts by weight:
178.76g of polyamic acid resin,
10g of dimethyl phthalate,
10g of erucamide,
Thermally conductive paste 124.77 g.
Wherein, the polyamic acid is prepared by sequentially adding 20.02g (0.10mol) of 4,4' -diaminodiphenyl ether and 21.81g (0.10mol) of pyromellitic dianhydride into 136.93g N, N-dimethylformamide for polymerization; the thermal conductive slurry was prepared by mixing 22.51g of alumina having a particle size of 1 μm with 100g N, N-dimethylformamide.
Comparative example 2 compared to example 1, a highly thermal conductive polyimide film was prepared in the same manner as in example 1, without using a surface modifier and an anti-settling agent.
The preparation method of the polyimide film of the comparative example includes the following steps:
(1) under the protection of nitrogen atmosphere, sequentially adding 20.02g (0.10mol) of 4,4' -diaminodiphenyl ether and 21.81g (0.10mol) of pyromellitic dianhydride into 136.93g N, N-dimethylformamide, and mechanically stirring at-20-30 ℃ for 3 hours to synthesize polyamide acid resin;
(2) 22.51g of alumina with the particle size of 1 mu m is mixed with 100g N, N-dimethylformamide, treated by a high-speed dispersion machine with the speed of 3000r/min for 2 hours, uniformly dispersed, and then put into a sand mill for grinding and modification for 2 hours to prepare heat-conducting slurry;
(3) defoaming the polyamic acid resin, blending the polyamic acid resin with heat-conducting slurry, 10g of dimethyl phthalate and 10g of erucamide, fully and uniformly mixing the mixture by a screw mixer, casting the mixture onto a steel belt, keeping the temperature at 120 ℃ for 10min to remove part of solvent, keeping the temperature at 150 ℃ for 10min, keeping the temperature at 200 ℃ for 10min, keeping the temperature at 250 ℃ for 10min, keeping the temperature at 320-380 ℃ for 10min, and stretching and imidizing the mixture to obtain the polyimide film.
The polyimide films prepared in examples 1 to 5 and comparative examples 1 to 2 were tested for their respective properties, and the test results are shown in table 1.
TABLE 1 comparison of the Properties of polyimide films obtained in inventive examples 1 to 5 and comparative examples 1 to 2
As shown in Table 1, the polyimide film prepared by the method of the present invention has the characteristics of high thermal conductivity and excellent mechanical properties, and is easy to machine and mold and suitable for industrial production.
Claims (7)
1. The polyimide film is characterized by being prepared by carrying out tape casting, imidization and stretching on a polyamic acid solution composition, wherein the polyamic acid solution composition is prepared by mixing the following components in parts by weight:
100-150 parts of polyamide acid resin,
5-20 parts of plasticizer,
0.5-10 parts of slipping agent,
50-125 parts of heat-conducting slurry;
the plasticizer comprises a first type of small molecule plasticizer and a second type of small molecule plasticizer; the first type of micromolecular plasticizer is aromatic dibasic acid ester and/or aliphatic dibasic acid ester; the second type of small molecular plasticizer is a triamide oligomer with the molecular weight of 100-3000;
the aromatic dibasic acid ester is at least one of dimethyl phthalate, diethyl phthalate, dibutyl phthalate, diallyl phthalate, dioctyl phthalate and diisooctyl phthalate;
the aliphatic dibasic acid ester is at least one of dioctyl sebacate, dioctyl oxalate and dibutyl sebacate;
the heat-conducting slurry comprises the following components in parts by weight:
10-50 parts of inorganic heat-conducting filler,
0.5-10 parts of surfactant,
0.5-10 parts of anti-settling agent,
50-90 parts of a polar solvent.
2. The polyimide film of claim 1 wherein the slip agent is at least one of oleamide, erucamide, octadecanamide.
3. The polyimide film according to claim 1, wherein the inorganic heat conductive filler is at least one of aluminum nitride, boron nitride and aluminum oxide, and the particle size of the inorganic heat conductive filler is 100nm to 5000 nm;
the surfactant is 4-aminopropyl methyl dimethoxy silane, 3-aminopropyl methyl diethoxy silane, 3-aminopropyl trimethoxy silane, 3-aminopropyl triethoxy silane, N- (2-aminoethyl) -3-aminopropyl methyl diethoxy silane, N- (2-aminoethyl) -3-aminopropyl methyl dimethoxy silane, at least one of N- (2-aminoethyl) -3-aminopropyltriethoxysilane, N- (2-aminoethyl) -3-aminopropyltrimethoxysilane, N- (piperazinylethyl) -3-aminopropylmethyldimethoxysilane, 3-divinyltriaminopropylmethyldimethoxysilane and 3-divinyltriaminopropyltrimethoxysilane;
the anti-settling agent is N-methyl pyrrolidone solution of polyamide wax and/or modified urea.
4. The polyimide film according to claim 1, wherein the polyamic acid resin comprises the following components in parts by weight:
10-20 parts of polyamide acid,
40-180 parts of a polar solvent;
the polyamic acid is prepared by performing polycondensation reaction on diamine and dianhydride in equal molar ratio in a polar solvent;
the dianhydride is at least one of pyromellitic dianhydride, 3,3',4,4' -biphenyltetracarboxylic dianhydride, 2,3,3',4' -diphenyl ether tetracarboxylic dianhydride, 3,3',4,4' -benzophenone tetracarboxylic dianhydride, bisphenol A type diether dianhydride, 2 '-bis [4- (3, 4-dicarboxyphenoxy) phenyl ] propane tetracarboxylic dianhydride and 2,2' -bis (3, 4-dicarboxyphenyl) hexafluoropropane tetracarboxylic dianhydride;
the diamine is at least one of 4,4' -diaminodiphenyl ether, 3,4' -diaminodiphenyl ether, p-phenylenediamine, o-phenylenediamine, m-phenylenediamine and 2,2' -bis [ (4-aminophenoxy) phenyl ] propane.
5. The polyimide film according to any one of claims 1 to 4, wherein the polar solvent is at least one of N-methylpyrrolidone, N-dimethylformamide, and N, N-dimethylacetamide.
6. A method for producing the polyimide film according to any one of claims 1 to 5, comprising the steps of:
defoaming polyamide acid resin, uniformly mixing with heat-conducting slurry, plasticizer and slipping agent to obtain polyamide acid solution composition, casting onto a steel belt, keeping the temperature of 100-120 ℃ for 10-20 min, keeping the temperature of 140-160 ℃ for 10-20 min, keeping the temperature of 180-220 ℃ for 10-20 min, keeping the temperature of 220-280 ℃ for 10-20 min, keeping the temperature of 320-380 ℃ for 10-20 min, and performing stretching imidization to obtain the polyimide film.
7. The method according to claim 6, wherein the method comprises the following steps: under the atmosphere of nitrogen, adding diamine and dianhydride in equal molar ratio into a polar solvent, and stirring for 4-6 hours at the temperature of-20-30 ℃ to obtain polyamide acid resin;
the preparation method of the heat-conducting slurry comprises the following specific operation steps: dispersing the inorganic heat-conducting filler, the surfactant, the anti-settling agent and the polar solvent uniformly by a high-speed dispersion machine, and then putting the mixture into a sand mill for grinding and modification to obtain the heat-conducting slurry.
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| JP7413659B2 (en) * | 2019-04-25 | 2024-01-16 | 住友ベークライト株式会社 | Resin compositions and electronic component structures |
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| CN110437614A (en) * | 2019-07-26 | 2019-11-12 | 宁波今山新材料有限公司 | The preparation method of formable polyimide film |
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| CN112409612B (en) * | 2020-09-30 | 2023-08-25 | 苏州尊尔光电科技有限公司 | Preparation method of high-solid-content low-viscosity polyamic acid solution |
| CN112500569B (en) * | 2021-02-04 | 2021-05-25 | 武汉柔显科技股份有限公司 | Polyimide precursor composition, polyimide film, laminated film, and display device |
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