CN113980313B - Preparation method of corona-resistant polyimide composite film and composite film - Google Patents
Preparation method of corona-resistant polyimide composite film and composite film Download PDFInfo
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- C08J2379/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
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Abstract
The invention relates to a preparation method of a corona-resistant polyimide composite film and the composite film. The preparation method comprises the following steps: bonding hydroxyl-substituted thiophenol to a titanium-containing nano material to obtain a modified titanium-containing nano material, generating noble metal nano particles on the modified titanium-containing nano material through a photoreduction process to obtain a titanium-containing nano material modified by the noble metal nano particles, and adding the titanium-containing nano material modified by the noble metal nano particles into a dianhydride precursor and a diamine precursor for in-situ polymerization to obtain a polyimide precursor composite material; preparing the polyimide precursor composite material into a polyimide precursor film by adopting a tape casting method, and further imidizing the polyimide precursor film to obtain the polyimide film. The polyimide film prepared by the invention not only has excellent dielectric property, but also has excellent corona resistance and mechanical property.
Description
Technical Field
The invention relates to a preparation method of a corona-resistant polyimide composite film and the composite film.
Background
Polyimide films have found wide use in various industrial sectors because of their good stability and dielectric properties. With the continuous expansion of the application field of polyimide films, the requirements of the industry on various properties of polyimide are higher and higher, for example, better corona resistance and dielectric property are required while mechanical properties are maintained.
It is known that doping inorganic particles can improve corona resistance of polyimide films. Typical doped inorganic particles are inorganic particles containing titanium or titanic acid, such as titanium dioxide particles, barium titanate particles, copper calcium titanate particles, and the like. However, the incorporation of these inorganic particles, particularly in large amounts, can result in a reduction in the dielectric loss properties of the polyimide film. The precious metal nanoparticles are adopted to carry out surface modification on the doped inorganic particles, so that the reduction degree of the dielectric loss performance of the polyimide film can be reduced. For example, Yang et al, in Chinese patent CN103755958A, disclose wrapping silver particles on the surface of calcium copper titanate ceramic particles and further prepare polyimide/calcium copper titanate coated silver nanoparticle composites and films with significantly improved dielectric constant and dielectric loss at a lower level than unmodified polyimide.
However, although the dielectric properties are improved by the noble metal particle modification, a new problem is caused: the corona resistance and mechanical properties of polyimide composite materials prepared by noble metal nanoparticle modification processes in the prior art are reduced.
Disclosure of Invention
The invention aims to solve the technical problem of providing an improved preparation method of a polyimide composite film aiming at the defects and shortcomings of the prior art, and the polyimide composite film prepared by the method has excellent dielectric property, corona resistance and mechanical property.
The invention also provides a polyimide composite film which not only has excellent dielectric property, but also has excellent corona resistance and mechanical property.
In order to solve the technical problems, the invention adopts a technical scheme as follows:
a preparation method of a corona-resistant polyimide composite film comprises the following steps:
1) bonding hydroxyl-substituted thiophenol to a titanium-containing nano material to obtain a modified titanium-containing nano material, wherein the titanium-containing nano material is one or a combination of more of titanium dioxide nano tubes, titanium dioxide nano particles, barium titanate nano particles or copper calcium titanate nano particles;
2) generating noble metal nano particles on the modified titanium-containing nano material through a photoreduction process to obtain the titanium-containing nano material modified by the noble metal nano particles, wherein the noble metal nano particles are chemically connected with the titanium-containing nano material through hydroxyl substituted thiophenol;
3) adding the titanium-containing nano material modified by the noble metal nano particles into a dianhydride precursor and a diamine precursor for in-situ polymerization to obtain a polyimide precursor composite material;
4) preparing the polyimide precursor composite material into a polyimide precursor film by adopting a tape casting method, and further imidizing the polyimide precursor film to obtain the polyimide film.
Preferably, the hydroxy-substituted thiophenol is a combination of one or more selected from 2-hydroxythiophenol, 3-hydroxythiophenol or 4-hydroxythiophenol.
Further, the mass ratio of the hydroxyl-substituted thiophenol to the titanium-containing nano material is 1-3: 100.
Further, in the step 1), the method for bonding the hydroxyl-substituted thiophenol to the titanium-containing nanomaterial comprises the following steps: mixing a titanium-containing nano material, hydroxyl substituted thiophenol and water, and then putting the mixture into a high-pressure container filled with argon protection to carry out heating treatment at the temperature of 60-80 ℃.
Further, the noble metal nano-particles are selected from Au, Ag or Pt nano-particles, and the particle size of the noble metal nano-particles is 10-60 nm.
Preferably, in the step 2), the photo-reduction process includes: firstly, heating a chloroauric acid solution, a silver nitrate solution or a chloroplatinic acid solution and the modified titanium-containing nano material in a high-pressure container filled with argon for protection at 50-70 ℃ to obtain a mixture, wherein the concentration of the chloroauric acid solution, the silver nitrate solution or the chloroplatinic acid solution is 2-15 mg/L; next, the mixture obtained above was placed under a xenon lamp of 200-400W for 2-6 hours of irradiation.
In the prior art, when inorganic particles containing titanium or titanic acid are modified by noble metal nanoparticles to prepare a polyimide film, graft modification is usually performed between the inorganic particles and the polyimide, and the dispersion and connection effects between the inorganic particles and the noble metal nanoparticles are neglected, so that the corona resistance of the polyimide film is influenced. The inventor finds out in a large number of experimental researches that chemical connection is carried out on the titanium-containing nano material and the noble metal nano particles through hydroxyl substituted thiophenol, so that the dispersion and connection effects between the titanium-containing nano material and the noble metal nano particles can be effectively improved, and finally, the polyimide composite film with excellent corona resistance and mechanical properties is obtained.
In one embodiment of the present invention, the titanium-containing nanomaterial is a titanium dioxide nanotube having a higher specific surface area and reactivity than other titanium-containing nanomaterials.
In some embodiments of the invention, the titanium dioxide nanotubes have a diameter of 15-55nm and a length of 200-500 nm.
In some embodiments of the invention, the titanium dioxide nanoparticles have a particle size of 50 to 100 nm.
In some embodiments of the invention, the barium titanate nanoparticles have a particle size of 150-300 nm.
In some embodiments of the invention, the copper calcium titanate nanoparticles have a particle size of 150-300 nm.
In some embodiments of the invention, the mass ratio of the titanium-containing nanomaterial to the noble metal nanoparticles is 1: 0.01 to 0.05, wherein the total amount of the two accounts for 10 to 20 percent of the total mass of the polyimide composite material.
In some embodiments of the invention, the titanium-containing nanomaterial modified with noble metal nanoparticles is subjected to silane coupling agent modification prior to the in situ polymerization.
Preferably, the silane coupling agent is selected from the group consisting of KH570, KH550 or KH 560.
In some embodiments, the dianhydride precursor is one or a combination of more selected from pyromellitic dianhydride, 4 '-hexafluoroisopropyl phthalic anhydride, bisphenol-a type dianhydride BPADA, and the diamine precursor is one or a combination of two selected from 4, 4' -diamino-2, 2 '-dimethyl-1, 1' -biphenyl or m-phenylenediamine PDA.
In some preferred embodiments, the molar ratio of dianhydride precursor to diamine precursor is from 0.98 to 1.05: 1.
the invention also provides a corona-resistant polyimide composite film product prepared by the preparation method, which has excellent mechanical properties and obviously improved corona resistance.
In some preferred embodiments according to the present invention, the corona resistant polyimide composite film has a corona resistance time of 460 hours or more at 20kHz and 1 kv.
In some preferred embodiments according to the present invention, the corona-resistant polyimide composite film has a tensile strength of 140 mpa or more at a thickness of 25 ± 0.2 cm.
In some preferred embodiments according to the present invention, the corona-resistant polyimide composite film has an elongation at break of 30% or more at a thickness of 25 ± 0.2 cm.
Further, the thickness of the polyimide film is 5-35 microns.
In one embodiment of the present invention, the corona resistant polyimide composite film further comprises a silane coupling agent. The titanium-containing nano material modified by the noble metal nano particles is subjected to surface grafting modification by the silane coupling agent, so that the dispersibility of the titanium-containing nano material in the polyimide film can be further improved.
Due to the application of the technical scheme, compared with the prior art, the invention has the following advantages:
1) the invention creatively adopts the hydroxyl-substituted thiophenol to chemically connect the titanium-containing nano material and the noble metal nano particles, thereby modifying and distributing the uniformly and stably distributed noble metal nano particles on the surface of the titanium-containing nano material, leading the noble metal nano particles to be hardly agglomerated on the titanium-containing nano material, and improving the dispersibility and the connection effect of the titanium-containing nano material and the noble metal nano particles.
2) The titanium-containing nano material modified by the noble metal nano particles is creatively used as a component of the polyimide composite film, so that the polyimide composite film has excellent mechanical property and corona resistance while maintaining good dielectric property.
Drawings
FIG. 1 is a TEM image of gold nanoparticle-modified titania nanotubes of example 1;
FIG. 2 is a TEM image of the gold nanoparticle-modified titania nanotubes of example 1 for EDS elemental analysis, in which black boxes are selected areas for EDS elemental analysis;
FIG. 3 is a graph of EDS elemental analysis of the region outlined in the black box of FIG. 2.
Detailed Description
The inventor finds that the polyimide composite film containing the noble metal nanoparticles in the prior art has poor corona resistance and reduced mechanical properties, mainly because the noble metal nanoparticles are easy to agglomerate and the connection effect between the noble metal nanoparticles and the doped inorganic particles is poor in the prior art. The inventor provides an improved preparation process based on a large number of experimental research bases, and successfully solves the problem.
The method comprises the steps of carrying out surface modification on the titanium-containing nano material by adopting hydroxyl-substituted thiophenol, connecting hydroxyl in the hydroxyl-substituted thiophenol with titanium atoms of the titanium-containing nano material, forming functional groups which are uniformly distributed and firmly connected on the surface of the titanium-containing nano material, and connecting noble metal nano particles through sulfydryl on the hydroxyl-substituted thiophenol, so that the uniformly distributed and stable noble metal nano particles are modified on the surface of the titanium-containing nano material, and thus, in the finally prepared polyimide film, the titanium-containing nano material and the noble metal nano particles are well dispersed and are firmly connected with each other. Experiments prove that the polyimide film prepared by the method has obviously improved corona resistance and mechanical properties.
The technical solutions of the present invention are described in detail below with reference to specific examples so that those skilled in the art can better understand and implement the technical solutions of the present invention, but the present invention is not limited to the scope of the examples.
Example 1
The polyimide film was prepared as follows:
1) preparing a titanium dioxide nanotube: in a high-pressure reaction kettle, according to the mass ratio of 1: 5 adding anatase phase titanium dioxide powder with the particle size of 50nm and NaOH solution with the concentration of 10M, sealing, and carrying out hydrothermal reaction for 72 hours at the temperature of 140 ℃; and after the reaction kettle is cooled, removing the white solid from the high-pressure reaction kettle, washing the white solid with 0.1M hydrochloric acid solution, washing the white solid with a large amount of deionized water until the pH value of an effluent solution is neutral, and drying the effluent solution at 80 ℃ to obtain the titanium dioxide nanotube.
2) Modification of the titanium dioxide nanotube: mixing titanium dioxide nanotubes, 4-hydroxythiophenol and deionized water according to the mass ratio of 100: 3: 2 and then putting the mixture into a high-pressure container filled with argon for protection, and heating the mixture for 24 hours at 70 ℃ to obtain the modified titanium dioxide nanotube.
3) Modifying the gold nanoparticles: 10 mg/mL chloroauric acid (HAuCl) was injected into a high-pressure vessel4) The mass ratio of the solution of chloroauric acid to the modified titanium dioxide nanotube is 3: 100. then, the high-pressure vessel was kept under an argon atmosphere and sealed, and heat-treated at 60 ℃ for 2 hours, after which the reaction mixture was kept stirred at room temperature and naturally cooled. Stirring the cooled reaction mixture, and irradiating the reaction mixture for 4 hours by using 300W xenon lamp ultraviolet light to obtain the modified titanium dioxide nano-particlesAnd (3) performing photo-reduction on the tube to generate gold nanoparticles, repeatedly washing the product with distilled water and ethanol, and drying at 80 ℃ to obtain the titanium dioxide nanotube modified by the gold nanoparticles.
4) Modification of a silane coupling agent: adding the titanium dioxide nanotube modified by the gold nanoparticles into a solution of KH570 silane coupling agent in absolute ethyl alcohol according to the mass fraction of 10% -20%, wherein the volume ratio of KH570 to absolute ethyl alcohol is 1: 10, carrying out ultrasonic dispersion treatment for 10 minutes; followed by an oil bath at 400 ℃ for 4 hours; and after the oil bath is finished, repeatedly cleaning the obtained floccule with absolute ethyl alcohol and deionized water, performing suction filtration, and naturally drying at room temperature to obtain the titanium dioxide nanotube modified by the silane coupling agent and modified by the gold nanoparticles.
5) Adding the titanium dioxide nanotube modified by the silane coupling agent modified gold nanoparticles into a DMF (dimethyl formamide) solution of pyromellitic dianhydride to ensure that the solid content of the added system is 10, and performing ultrasonic dispersion treatment for 1 hour in water bath at the temperature of 80 ℃; adding m-Phenylenediamine (PDA) accounting for 5% of the mass fraction of the system, and uniformly stirring and dispersing; after the PDA is completely dissolved, slowly adding bisphenol A type dianhydride BPADA into the mixed solution, wherein the molar ratio of the added PDA to the added BPADA is 1: 1.01; continuously stirring for 4 hours to obtain polyimide precursor polyamide acid (PAA) solution; the polyamic acid (PAA) was sonicated for 10 minutes and then placed in a vacuum oven to remove air bubbles from the solution under vacuum.
6) Preparing a polyimide precursor polyamide acid (PAA) solution by using a tape casting method to obtain a polyimide precursor film, and imidizing the polyimide precursor film to obtain the polyimide film with the thickness of 25.1 microns.
A TEM image of the titanium dioxide nanotube modified by the gold nanoparticles is shown in fig. 1, wherein the gold nanoparticles are granular, and the gold nanoparticles are successfully modified on the titanium dioxide nanotube. Fig. 2 is a TEM image corresponding to the EDS elemental analysis, in which a black portion is a background, a white portion is a titanium dioxide nanotube sample modified by gold nanoparticles, and EDS elemental analysis is performed on a region selected by a black frame in fig. 2, and an elemental analysis diagram is shown in fig. 3.
Example 2
The process for preparing the polyimide composite film is basically the same as that of example 1 except that: and 3) replacing the chloroauric acid solution with a silver nitrate solution.
Example 3
The process for preparing the polyimide composite film is basically the same as that of example 1 except that: and 3) replacing the chloroauric acid solution with a chloroplatinic acid solution.
Example 4
The process for preparing the polyimide composite film is basically the same as that of example 1 except that: in the step 2), 2-hydroxythiophenol is adopted to replace 4-hydroxythiophenol.
Example 5
The process for preparing the polyimide composite film is basically the same as that of example 1 except that: in the step 2), 3-hydroxythiophenol is adopted to replace 4-hydroxythiophenol.
Example 6
The process for preparing the polyimide film is substantially the same as that of example 1 except that: step 1) is not carried out, and anatase-phase titanium dioxide nano-particles with the particle size of 50nm are directly substituted for the titanium dioxide nano-tubes in the step 2).
Example 7
The process for preparing the polyimide film is substantially the same as that of example 1 except that: step 1) was not performed, and the titanium dioxide nanotubes in step 2) were replaced with copper calcium titanate nanoparticles having a particle size of 50 nm.
Comparative example 1
The process for preparing the polyimide film is substantially the same as that of example 1 except that: step 2) is not carried out, namely 4-hydroxythiophenol is not adopted to modify the titanium dioxide nanotube.
Comparative example 2
The process for preparing the polyimide film is substantially the same as that of example 1 except that: in the step 2), dopamine is adopted to replace 4-hydroxythiophenol.
Comparative example 3
Adding m-Phenylenediamine (PDA) accounting for 5% of the mass fraction of the DMF solution into the DMF solution of pyromellitic dianhydride, and uniformly stirring and dispersing; after the PDA is completely dissolved, slowly adding bisphenol A type dianhydride BPADA into the mixed solution, wherein the molar ratio of the added PDA to the added BPADA is 1: 1.01; continuously stirring for 4 hours to obtain polyimide precursor polyamide acid (PAA) solution; the polyamic acid (PAA) was sonicated for 10 minutes and then placed in a vacuum oven to remove air bubbles from the solution under vacuum. The polyimide film is prepared from polyimide precursor polyamide acid (PAA) solution by a tape casting method, and the thickness of the polyimide film is 10 microns.
Comparative example 4
The process for preparing a polyimide film is substantially the same as in example 6 except that: step 2) is not performed, i.e. the titanium dioxide nanoparticles are not modified with 4-hydroxythiophenol.
Comparative example 5
The process for preparing a polyimide film is substantially the same as in example 7 except that: step 2) is not performed, i.e. the titanium dioxide nanoparticles are not modified with 4-hydroxythiophenol.
The films of examples 1 to 7 and comparative examples 1 to 5 were subjected to corona resistance tests (test parameters: 20kHz, 1kv) in accordance with GB/T22689-2008/IEC60304: 1991; the samples were subjected to mechanical property testing according to GB/T13542.2-2009 at a tensile speed of 50 mm/min, the results are shown in Table 1.
As shown by comparison in Table 1, the corona resistance of the polyimide film is obviously improved compared with that of the common film which does not adopt 4-hydroxythiophenol to modify the titanium dioxide nanotube or adopts dopamine containing hydroxyl and amino to modify the titanium dioxide nanotube. Therefore, the corona resistance of the polyimide film of the present invention is significantly higher than that of a conventional polyimide film.
The above embodiments are merely illustrative of the technical ideas and features of the present invention, and the purpose thereof is to enable those skilled in the art to understand the contents of the present invention and implement the present invention, and not to limit the protection scope of the present invention. All equivalent changes and modifications made according to the spirit of the present invention should be covered within the protection scope of the present invention.
The endpoints of the ranges and any values disclosed herein are not limited to the precise range or value, and such ranges or values should be understood to encompass values close to those ranges or values. For ranges of values, between the endpoints of each of the ranges and the individual points, and between the individual points may be combined with each other to give one or more new ranges of values, and these ranges of values should be considered as specifically disclosed herein.
Claims (10)
1. A preparation method of a corona-resistant polyimide composite film is characterized by comprising the following steps: the preparation method comprises the following steps:
1) bonding hydroxyl-substituted thiophenol to a titanium-containing nano material to obtain a modified titanium-containing nano material, wherein the titanium-containing nano material is one or a combination of more of titanium dioxide nano tubes, titanium dioxide nano particles, barium titanate nano particles or copper calcium titanate nano particles, the feeding mass ratio of the hydroxyl-substituted thiophenol to the titanium-containing nano material is 1-3:100, and the method for bonding the hydroxyl-substituted thiophenol to the titanium-containing nano material comprises the following steps: mixing the titanium-containing nano material, hydroxyl-substituted thiophenol and water, then putting the mixture into a high-pressure container filled with argon protection, and heating at 60-80 ℃;
2) generating noble metal nanoparticles on the modified titanium-containing nano material through a photoreduction process to obtain the titanium-containing nano material modified by the noble metal nanoparticles, wherein the noble metal nanoparticles are chemically connected with the titanium-containing nano material through hydroxyl substituted thiophenol, and the mass ratio of the titanium-containing nano material to the noble metal nanoparticles is 1: 0.01-0.05, wherein the total mass of the two accounts for 10-20% of the total mass of the corona-resistant polyimide composite film;
3) adding the titanium-containing nano material modified by the noble metal nano particles into dianhydride and diamine for in-situ polymerization to obtain a polyimide precursor composite material, wherein the molar ratio of the dianhydride to the diamine is (0.98-1.05): 1;
4) preparing the polyimide precursor composite material into a polyimide precursor film by adopting a tape casting method, and imidizing the polyimide precursor film to obtain the polyimide film.
2. The method for preparing the corona-resistant polyimide composite film according to claim 1, wherein: the hydroxyl-substituted thiophenol is one or more of 2-hydroxythiophenol, 3-hydroxythiophenol or 4-hydroxythiophenol.
3. The method for preparing the corona-resistant polyimide composite film according to claim 1, wherein: the noble metal nanoparticles are selected from Au, Ag or Pt nanoparticles; and/or the particle size of the noble metal nano-particles is 10-60 nm.
4. The method for preparing a corona-resistant polyimide composite film according to claim 1 or 3, wherein: in the step 2), the photo-reduction process includes: firstly, heating a chloroauric acid solution, a silver nitrate solution or a chloroplatinic acid solution and the modified titanium-containing nano material in a high-pressure container filled with argon protection at 50-70 ℃ to obtain a mixture, wherein the concentration of the chloroauric acid solution, the silver nitrate solution or the chloroplatinic acid solution is 2-15 mg/L; next, the mixture obtained above was placed under a xenon lamp of 200-400W for 2-6 hours of irradiation.
5. The method for preparing the corona-resistant polyimide composite film according to claim 1, wherein: the diameter of the titanium dioxide nanotube is 15-55nm, and the length is 200-500 nm; and/or the particle size of the titanium dioxide nano-particles is 50-100 nm; the particle size of the barium titanate nano-particles is 150-300 nm; and/or the particle size of the copper calcium titanate nano-particles is 150-300 nm.
6. The method for preparing the corona-resistant polyimide composite film according to claim 1, wherein: the dianhydride is one or more selected from pyromellitic dianhydride, 4 '-hexafluoroisopropyl phthalic anhydride and bisphenol A dianhydride BPADA, and the diamine is one or two selected from 4, 4' -diamino-2, 2 '-dimethyl-1, 1' -biphenyl or m-phenylenediamine PDA.
7. The method for preparing the corona-resistant polyimide composite film according to claim 1, wherein: before the in-situ polymerization, the titanium-containing nano material modified by the noble metal nano particles is modified by a silane coupling agent.
8. The method for preparing the corona-resistant polyimide composite film according to claim 7, wherein: the silane coupling agent is one or more selected from KH570, KH550 or KH 560.
9. A corona-resistant polyimide composite film prepared by the method for preparing the corona-resistant polyimide composite film as claimed in any one of claims 1 to 8.
10. The corona resistant polyimide composite film of claim 9, wherein: the corona resistant polyimide composite film has corona resistant time of more than 460 hours under the conditions of 20kHz and 1 kv.
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