CN111471300A - Heat-conducting polyimide insulating film and preparation method thereof - Google Patents
Heat-conducting polyimide insulating film and preparation method thereof Download PDFInfo
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- C08J5/18—Manufacture of films or sheets
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Abstract
The invention discloses a heat-conducting polyimide insulating film and a preparation method thereof. Firstly, preparing a two-dimensional carbon nitride nanosheet with high thermal conductivity and electrical insulation by taking melamine as a precursor; then introducing the carbon nitride nanosheet into a polyamic acid solution and uniformly mixing; and finally, transferring the dispersion liquid onto a plane board, and obtaining the heat-conducting polyimide insulating film through curing and imidization treatment, wherein the carbon nitride nanosheets are arranged in the polyimide film in a layer-by-layer laying manner. The invention not only provides a simple process route to realize the in-plane arrangement of the nanosheet material in the polyimide film, but also provides the polyimide insulating film which has excellent thermal stability, flexibility, electrical insulation and low thermal expansion coefficient and has high application value in the field of thermal management of electronic devices.
Description
Technical Field
The invention belongs to the technical field of polyimide nano composite films, and particularly relates to a heat-conducting polyimide insulating film and a preparation method thereof.
Background
With the development of electronic products toward multi-function, miniaturization and even flexible direction, higher requirements are put forward on the internal electronic components, mainly represented by size reduction, high integration level and high power density. However, such high package level power densities will result in rapid increases in heat flux per unit area causing severe heat build up problems resulting in material degradation, malfunction, reduced reliability and even component damage. Effective thermal management is then critical to the proper operation and long-term stability of the electronic device. Polyimide films have been widely used as flexible substrate materials in the field of electronic packaging due to their excellent high and low temperature resistance, electrical insulation properties, dimensional stability, and low thermal expansion coefficient and dielectric constant. However, as a heat insulating material (thermal conductivity ≈ 0.2 Wm)-1K-1) Polyimide films generally need to be combined with highly thermally conductive inorganic fillers to improve their thermal conductivity.
At present, the heat-conducting performance of the polymer is greatly improved by introducing various heat-conducting fillers, such as graphene, carbon nano tubes, boron nitride, aluminum oxide, silicon carbide and the like. However, for polyimide insulating films, the selection of the thermally conductive filler has certain specificity: (1) as for the conductive carbon material, although it can impart excellent heat conductive properties to the polyimide film, good electrical insulating properties of the polyimide film are often impaired; (2) although good thermal conductivity and electrical insulation of polyimide films can be simultaneously achieved by the ceramic filler, due to the large size, rigid structure and chemical inertness of the ceramic filler, the flexibility and easy processing characteristics of the PI film are seriously affected. Therefore, finding a heat conductive filler with nanoscale and capable of greatly improving the heat conductivity of the polyimide film becomes a hot spot of current research.
Disclosure of Invention
The invention aims to overcome the defects in the prior art and provides a heat-conducting polyimide insulating film.
Another technical problem to be solved by the present invention is to provide a method for preparing a heat conductive polyimide insulating film.
In order to solve the technical problem, the technical scheme is that the heat-conducting polyimide insulating film is composed of a polyimide film and carbon nitride nanosheets uniformly dispersed in the polyimide film in a mass ratio of 100 (1-20), and the carbon nitride nanosheets are arranged in the polyimide film in a layer-by-layer laying mode.
As a further improvement of the heat conductive polyimide insulating film:
preferably, the carbon nitride nanosheet is one or two or more of an element-doped carbon nitride nanosheet, a carbon nitride nanosheet grafted with different chemical components, and a carbon nitride nanosheet with different molecular structures.
As a further technical scheme of the element-doped carbon nitride nanosheet, the element-doped carbon nitride nanosheet is formed by doping one or two or more of nitrogen, oxygen, phosphorus, carbon, silver and copper in the carbon nitride nanosheet.
In order to solve another technical problem of the present invention, a method for preparing a heat conductive polyimide insulating film is provided, which comprises the following steps:
s1, preparing carbon nitride nanosheets: placing the carbon nitride precursor in a high-temperature resistant container, placing the high-temperature resistant container in a high-temperature furnace, heating the temperature from room temperature to 500-600 ℃ in a gradient heating mode, wherein the heating speed is 1-10 ℃/min, and then keeping the temperature for more than 2 hours to prepare bulk carbon nitride;
further processing the bulk carbon nitride by any one of an ultrasonic stripping method, a small molecule intercalation stripping method and a thermal etching method to prepare carbon nitride nanosheets;
s2, preparing a precursor mixed solution: adding 1-20 parts by mass of the prepared carbon nitride nanosheet into 700 parts by mass of 500-one organic solvent, performing ultrasonic dispersion, adding a polyimide precursor solution with the solid content of 5-25%, wherein the polyimide precursor solution contains 100 parts by mass of a polyimide precursor, and stirring until uniform mixing is performed to prepare a precursor mixed solution;
s3, preparing a heat-conducting polyimide insulating film: and (4) transferring the precursor mixed solution prepared in the step (S2) to a planar substrate by using a film forming method, curing and imidizing, naturally cooling to room temperature, and then placing the planar substrate in water to strip the heat-conducting polyimide insulating film.
The preparation method of the heat-conducting polyimide insulating film is further improved as follows:
preferably, the carbon nitride precursor in step S1 is one or two or more of melamine, cyanamide, and dicyandiamide.
Preferably, the ultrasonic peeling method in step S1 includes the specific steps of: dispersing 1-30 parts by mass of block carbon nitride in 1000 parts by mass of water, carrying out ultrasonic treatment for 1-24 hours, centrifuging or filtering the upper-layer colloidal solution to obtain a precipitate, and drying the precipitate to obtain the carbon nitride nanosheet.
Preferably, the small molecule intercalation and exfoliation method in step S1 includes the specific steps of: dispersing 5-20 parts by mass of block carbon nitride in 100 parts by mass of concentrated sulfuric acid with the concentration of 70-98 wt%, stirring for 1-8h, adding the stirred mixture into water, performing ultrasonic treatment for 1-12h, centrifuging or filtering the upper-layer colloidal solution to obtain a precipitate, cleaning the precipitate to be neutral, and drying to obtain the carbon nitride nanosheet.
Preferably, the thermal etching method in step S1 includes the specific steps of: placing the bulk carbon nitride on a high-temperature-resistant planar substrate, transferring the planar substrate into a high-temperature furnace, heating the planar substrate to 400-550 ℃ from room temperature in a gradient heating mode at a heating speed of 1-10 ℃/min, and then keeping the temperature for more than 30min to obtain the carbon nitride nanosheet.
Preferably, after step S1 and before step S2, the carbon nitride nanosheets are modified to produce element-doped carbon nitride nanosheets, different chemical component-grafted carbon nitride nanosheets, or different molecular structure carbon nitride nanosheets.
As a further technical scheme for modifying the carbon nitride nanosheet, the element-doped carbon nitride nanosheet is prepared by one or more of atmosphere adjustment, in-situ deposition and electrostatic attraction; the carbon nitride nanosheets grafted with different chemical components are prepared by one or more of electrostatic attraction, hydrogen bonding, pi-pi conjugation and in-situ polymerization; the carbon nitride nanosheets with different molecular structures are prepared by adjusting the atmosphere and controlling the heating procedure.
Preferably, the organic solvent in step S2 is one or two of N, N-dimethylformamide and N, N-dimethylacetamide.
Preferably, the polyimide precursor in step S2 is polyamic acid.
Preferably, the film forming method in step S3 is any one of a dipping method, a casting method, and a biaxial stretching method.
Preferably, the curing and imidizing treatment in step S3 includes the following specific steps: and carrying out heat treatment on the planar substrate loaded with the precursor mixed solution at the temperature of between 40 and 120 ℃ for more than 30min for curing treatment, transferring the planar substrate subjected to curing treatment into a high-temperature furnace, heating to the temperature of between 250 and 400 ℃, wherein the heating speed is 1 to 5 ℃/min, and carrying out heat treatment at the temperature for more than 30 min.
Compared with the prior art, the invention has the beneficial effects that:
1) tests show that compared with the existing heat conducting filler, the heat conductivity of the polymer can be improved by 2-6 times under the condition of low filling, the obtained polyimide insulating film has excellent thermal stability, flexibility, electric insulation and low thermal expansion coefficient, and the polyimide insulating film has high application value in the field of heat management of electronic devices.
2) The preparation method of the heat-conducting polyimide insulating film overcomes the defects of time consumption, high cost and complex operation in the orientation of the nanosheets in the prior art, the carbon nitride nanosheets are used as heat-conducting fillers for the first time, so that the heat conductivity of the polyimide insulating film is improved, and the excellent mechanical flexibility and electrical insulation performance of the polyimide film are still maintained while the heat conductivity of the polyimide film is improved due to the fact that the carbon nitride nanosheets have the graphene-like flexible layered structure and the electrical insulation performance; the preparation process is simple to operate, is easy to realize large-scale production of the heat-conducting polyimide insulating film, does not need to carry out chemical modification on the carbon nitride nanosheet, and does not involve harsh reaction conditions.
Drawings
Fig. 1 is a Transmission Electron Microscope (TEM) picture of carbon nitride nanosheets.
Fig. 2(a) is a Scanning Electron Microscope (SEM) image of a cross section of a pure polyimide film.
Fig. 2 (b) is a Scanning Electron Microscope (SEM) picture of a cross section of the thermally conductive polyimide insulating film prepared in example 1.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more clearly understood, the present invention is further described in detail below with reference to the accompanying drawings and embodiments, and all other embodiments obtained by a person of ordinary skill in the art based on the embodiments of the present invention without creative efforts belong to the protection scope of the present invention.
Example 1
A preparation method of a heat-conducting polyimide insulating film comprises the following steps:
(1) preparing carbon nitride nanosheets: weighing 10g of melamine powder, placing the melamine powder in an alumina crucible, transferring the crucible to a muffle furnace for heating, wherein the heating procedure is to heat the melamine powder from 20 ℃ to 500 ℃ at the speed of 2.5 ℃/min, then to heat the melamine powder to 550 ℃ at the speed of 1 ℃/min, keeping the temperature for 4h at 550 ℃, and naturally cooling the melamine powder to room temperature to obtain a yellow product, namely the bulk carbon nitride. Then, 0.4g of bulk carbon nitride is weighed and placed on a glass plate, the glass plate is transferred into a muffle furnace to be heated to 500 ℃ from room temperature at the speed of 5 ℃/min, the temperature is kept for 2h, and the product obtained after natural cooling to room temperature is the carbon nitride nanosheet.
(2) The preparation method of the heat-conducting polyimide insulating film precursor dispersion liquid comprises the steps of adding 10mg of carbon nitride nanosheets into 6m L of N, N-dimethylformamide, ultrasonically dispersing for 30min, then adding 5.6g of polyamic acid solution with the solid content of 18%, and continuously stirring for 3 h.
(3) Preparing a heat-conducting polyimide insulating film: pouring the polyimide insulating film precursor solution in the step (2) on a clean quartz glass substrate, and placing the quartz glass substrate in a vacuum oven at 80 ℃ for 4h for curing; then the polyimide insulating film is transferred into a muffle furnace to be heated from 80 ℃ to 300 ℃ at the speed of 2 ℃/min and is kept at the temperature for 1 h; and after naturally cooling to room temperature, placing the quartz substrate loaded with the polyimide insulating film in water to strip the heat-conducting polyimide insulating film.
Performing a Transmission Electron Microscope (TEM) on the carbon nitride nanosheet prepared in the step (1), wherein the result is shown in FIG. 1; as can be seen from fig. 1, the carbon nitride nanosheet exhibits a nanosheet structure, wherein the nanosheet has a lateral dimension of about 1.6 μm.
Scanning Electron Microscope (SEM) images of cross sections of the pure polyimide film and the thermally conductive polyimide insulating film prepared in step (3), respectively, are shown in fig. 2(a) and (b). As can be seen from fig. 2, the pure polyimide film has a smooth and dense cross section, whereas the cross section of the heat-conducting polyimide insulating film is rough, and the carbon nitride nanosheets are arranged in the polyimide film in a layer-by-layer manner.
Example 2
The preparation method was the same as example 1, except that 50mg of carbon nitride nanosheets were added to 6m L of N, N-dimethylformamide in step (2) as a comparative example to example 1.
Example 3
The preparation method was the same as example 1, except that 100mg of carbon nitride nanosheets were added to 6m L of N, N-dimethylformamide in step (2) as a comparative example to example 1.
Example 4
The preparation method was the same as example 1, except that 200mg of carbon nitride nanosheets were added to 6m L of N, N-dimethylformamide in step (2) as a comparative example to example 1.
The heat conductive polyimide insulating films prepared in examples 1 to 4 were subjected to performance tests, respectively, and the results are shown in table 1;
TABLE 1 comparison of Properties of pure polyimide film and polyimide insulating films prepared in examples 1 to 4
The test results in table 1 show that the thermal conductivity of the polyimide insulating film is continuously increased with the increase of the content of the carbon nitride nanosheets, which indicates that the added carbon nitride nanosheet material is used for constructing a thermal conduction path in the polyimide insulating film; in addition, it is worth noting that with the introduction of the carbon nitride nanosheets, the volume resistivity, the initial decomposition temperature and the thermal expansion coefficient of the polyimide insulating film do not fluctuate greatly, indicating that the introduction of a small amount of carbon nitride nanosheets does not have an adverse effect on the excellent overall performance of the polyimide film. The polyimide insulating film has excellent thermal stability, flexibility, electrical insulation and low thermal expansion coefficient, and has high application value in the field of thermal management of electronic devices.
It should be understood by those skilled in the art that the foregoing is only illustrative of several embodiments of the invention, and not of all embodiments. It should be noted that many variations and modifications are possible to those skilled in the art, and all variations and modifications that do not depart from the gist of the invention are intended to be within the scope of the invention as defined in the appended claims.
Claims (14)
1. A heat-conducting polyimide insulating film is characterized by comprising a polyimide film and carbon nitride nanosheets uniformly dispersed in the polyimide film in a mass ratio of 100 (1-20), wherein the carbon nitride nanosheets are arranged in the polyimide film in a layer-by-layer laying mode.
2. The heat conductive polyimide insulating film according to claim 1, wherein the carbon nitride nanosheets are one or two or more of element-doped carbon nitride nanosheets, carbon nitride nanosheets grafted with a different chemical composition, and carbon nitride nanosheets of a different molecular structure.
3. The heat conductive polyimide insulating film according to claim 2, wherein the element-doped carbon nitride nanosheets are carbon nitride nanosheets doped with one or two or more of nitrogen, oxygen, phosphorus, carbon, silver, and copper.
4. A method for preparing a heat conductive polyimide insulating film according to any one of claims 1 to 3, comprising the steps of:
s1, preparing carbon nitride nanosheets: placing the carbon nitride precursor in a high-temperature resistant container, placing the high-temperature resistant container in a high-temperature furnace, heating the temperature from room temperature to 500-600 ℃ in a gradient heating mode, wherein the heating speed is 1-10 ℃/min, and then keeping the temperature for more than 2 hours to prepare bulk carbon nitride;
further processing the bulk carbon nitride by any one of an ultrasonic stripping method, a small molecule intercalation stripping method and a thermal etching method to prepare carbon nitride nanosheets;
s2, preparing a precursor mixed solution: adding 1-20 parts by mass of the prepared carbon nitride nanosheet into 700 parts by mass of 500-one organic solvent, performing ultrasonic dispersion, adding a polyimide precursor solution with the solid content of 5-25%, wherein the polyimide precursor solution contains 100 parts by mass of a polyimide precursor, and stirring until uniform mixing is performed to prepare a precursor mixed solution;
s3, preparing a heat-conducting polyimide insulating film: and (4) transferring the precursor mixed solution prepared in the step S2 to a planar substrate by using a film forming method, carrying out curing and imidization treatment, naturally cooling to room temperature, and then placing the planar substrate in water to strip the heat-conducting and insulating polyimide nano composite film.
5. The method of claim 4, wherein the carbon nitride precursor in step S1 is one or two or more selected from melamine, cyanamide, and dicyandiamide.
6. The method for preparing a heat conductive polyimide insulating film according to claim 4, wherein the ultrasonic peeling method in step S1 comprises the following specific steps: dispersing 1-30 parts by mass of block carbon nitride in 1000 parts by mass of water, carrying out ultrasonic treatment for 1-24 hours, centrifuging or filtering the upper-layer colloidal solution to obtain a precipitate, and drying the precipitate to obtain the carbon nitride nanosheet.
7. The method for preparing a heat-conducting polyimide insulating film according to claim 4, wherein the small molecule intercalation and exfoliation method in step S1 includes the following specific steps: dispersing 5-20 parts by mass of block carbon nitride in 100 parts by mass of concentrated sulfuric acid with the concentration of 70-98 wt%, stirring for 1-8h, adding the stirred mixture into water, performing ultrasonic treatment for 1-12h, centrifuging or filtering the upper-layer colloidal solution to obtain a precipitate, cleaning the precipitate to be neutral, and drying to obtain the carbon nitride nanosheet.
8. The method for preparing a heat conductive polyimide insulating film according to claim 4, wherein the thermal etching method in step S1 comprises the following specific steps: placing the bulk carbon nitride on a high-temperature-resistant planar substrate, transferring the planar substrate into a high-temperature furnace, heating the planar substrate to 400-550 ℃ from room temperature in a gradient heating mode at a heating speed of 1-10 ℃/min, and then keeping the temperature for more than 30min to obtain the carbon nitride nanosheet.
9. The method for preparing a heat-conducting polyimide insulating film according to claim 4, wherein the carbon nitride nanosheets are modified after step S1 and before step S2 to produce element-doped carbon nitride nanosheets, different chemical component-grafted carbon nitride nanosheets, or different molecular structure carbon nitride nanosheets.
10. The method for preparing a heat-conducting polyimide insulating film according to claim 9, wherein the element-doped carbon nitride nanosheet is prepared by one or more of atmosphere conditioning, in-situ deposition, and electrostatic attraction; the carbon nitride nanosheets grafted with different chemical components are prepared by one or more of electrostatic attraction, hydrogen bonding, pi-pi conjugation and in-situ polymerization; the carbon nitride nanosheets with different molecular structures are prepared by adjusting the atmosphere and controlling the heating procedure.
11. The method of claim 4, wherein the organic solvent in step S2 is one or both of N, N-dimethylformamide and N, N-dimethylacetamide.
12. The method of claim 4, wherein the polyimide precursor in step S2 is polyamic acid.
13. The method of claim 4, wherein the film forming process in step S3 is any one of dipping, casting, and biaxial stretching.
14. The method for preparing a heat conductive polyimide insulating film according to claim 4, wherein the curing and imidizing treatment in step S3 comprises the following specific steps: and carrying out heat treatment on the planar substrate loaded with the precursor mixed solution at the temperature of between 40 and 120 ℃ for more than 30min for curing treatment, transferring the planar substrate subjected to curing treatment into a high-temperature furnace, heating to the temperature of between 250 and 400 ℃, wherein the heating speed is 1 to 5 ℃/min, and carrying out heat treatment at the temperature for more than 30 min.
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