CN115505151A - Low-dielectric-constant super-crosslinked polymer/polyimide composite film used under high frequency, preparation method and application - Google Patents
Low-dielectric-constant super-crosslinked polymer/polyimide composite film used under high frequency, preparation method and application Download PDFInfo
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- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/1003—Preparatory processes
- C08G73/1007—Preparatory processes from tetracarboxylic acids or derivatives and diamines
- C08G73/1028—Preparatory processes from tetracarboxylic acids or derivatives and diamines characterised by the process itself, e.g. steps, continuous
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- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/1039—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors comprising halogen-containing substituents
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- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/1067—Wholly aromatic polyimides, i.e. having both tetracarboxylic and diamino moieties aromatically bound
- C08G73/1071—Wholly aromatic polyimides containing oxygen in the form of ether bonds in the main chain
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- C08J2379/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen, or carbon only, not provided for in groups C08J2361/00 - C08J2377/00
- C08J2379/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
- C08J2379/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
Abstract
The invention provides a low dielectric constant super cross-linked polymer/polyimide composite film used under high-frequency working condition, a preparation method and application thereof, the invention mixes diaminodiphenyl ether, hexafluoro-isopropylidene diphthalic anhydride and aprotic solvent, carries out polymerization reaction to generate polyamide acid, adds the super cross-linked polymer, and carries out step heating amidation treatment to obtain the polyimide composite film; the mass content of the hypercrosslinked polymer in the composite membrane is 5-20%. According to the invention, the super-crosslinked polymer is added in the reaction process, so that the super-crosslinked polymer is more uniformly dispersed in the composite film, the doping amount of the super-crosslinked polymer is controlled, the dielectric constant of the composite film under a high-frequency working condition can be reduced, and meanwhile, the better thermal stability and mechanical property are kept. The prepared composite film can be applied to the fields of integrated circuits, microelectronics and insulating materials.
Description
Technical Field
The invention relates to the field of high molecules, in particular to a low-dielectric-constant super-crosslinked polymer/polyimide composite film used under high frequency, a preparation method and application.
Background
Polyimide (PI) is a high-performance polymer material obtained by condensation reaction of dibasic anhydride and diamine, and the molecular chain of the Polyimide (PI) is composed of repeat units containing imide rings. The aromatic polyimide has higher heat resistance, mechanical strength and chemical stability, because the repeating unit of a molecular chain has the conjugated effect of aromatic heterocyclic rings and nitrogen-containing five-membered heterocyclic rings, and the electron transfer complexing effect can be formed in molecules and among molecules. The applications of polyimide in the field of microelectronics mainly include the following aspects: interlayer insulating materials, photosensitive polyimide, flexible printed circuit boards, and the like. The conventional PI film has excellent electrical insulation, heat resistance and low dielectric constant (about 3.5, 10) 3 Hz) and corrosion resistance, which are the main insulating substrates of the current flexible printed circuit boards, however, low dielectric constant (less than 3) and even ultra-low dielectric constant (less than 2.2) insulating films are critical to ensure high speed, low delay and low loss transmission of electromagnetic signals due to the increase of 5G communication frequency. The high dielectric constant of the conventional PI film is difficult to meet the requirement of (ultra) low dielectric constant, and the dielectric loss of the PI film in a high frequency range is serious. Therefore, it is necessary to develop a high temperature resistant PI with a low dielectric constant suitable for a high frequency band.
In order to reduce the dielectric properties of the PI, groups are often introduced to reduce the overall polarity of the polymer, or low dielectric constant inorganic fillers are added to the PI to reduce the dielectric constant of the PI. However, the effect of reducing the dielectric constant in a high frequency band is often not sufficiently remarkable by introducing a group modification; however, the introduction of inorganic fillers tends to cause interfacial problems due to the difference in the structure between inorganic materials and organic materials. Although other modifications have been reported, they often fail to achieve a good balance between high frequency, low dielectric constant, high temperature resistance, and mechanical properties.
Disclosure of Invention
In order to solve the technical problems, the invention provides a polyimide composite film used under a high-frequency working condition, a preparation method and application thereof. Diamine monomers and dianhydride monomers are used as raw materials to prepare precursor polyamic acid, a super-crosslinked polymer and the precursor polyamic acid are uniformly mixed by a physical blending method to prepare a polyamic acid composite solution containing the super-crosslinked polymer, and then the temperature is increased in a step manner to carry out amidation reaction. The polyimide composite film prepared by the invention has extremely low dielectric constant under high-frequency working conditions, and has excellent thermal stability and mechanical strength.
In order to achieve the above purpose, the invention provides the following technical scheme:
the invention provides a preparation method of a low-dielectric-constant super-crosslinked polymer/polyimide composite film used under high frequency, which comprises the following specific steps:
(1) Mixing diaminodiphenyl ether, hexafluoro-isopropylene diphthalic anhydride and aprotic solvent by a physical blending method, and carrying out polymerization reaction to obtain precursor polyamic acid;
(2) Adding a super cross-linked polymer into a precursor polyamic acid solution, and physically blending to obtain a polyamic acid composite solution containing the super cross-linked polymer;
(3) And coating the polyamic acid composite solution containing the super-crosslinked polymer on a glass plate, heating in a stepped manner, carrying out amidation reaction, peeling from the glass plate, and drying to obtain the low-dielectric-constant super-crosslinked polymer/polyimide composite film used under high frequency.
Preferably, the mass ratio of the diaminodiphenyl ether to the hexafluoroisopropylidene diphthalic anhydride is 1: (2.3-2.5).
Preferably, the solvent includes one of N, N-dimethylformamide, N-dimethylacetamide and N-methylpyrrolidone.
Preferably, the ratio of the diaminodiphenyl ether to the solvent is 1g: (9-10) mL.
Preferably, the polymerization reaction temperature is-5 ℃, the subsequent polymerization temperature is room temperature, and the polymerization reaction time is 6-8 h.
Preferably, the mass content of the hypercrosslinked polymer in the composite membrane is 5-20%.
Preferably, the physical blending method includes mechanical stirring, magnetic stirring, and ultrasonic dispersion.
Preferably, the hypercrosslinked polymer is one of 4,4 '-bis (chloromethyl) -1,1' -biphenyl hypercrosslinked polymer and 1, 4-bis (chloromethyl) phenyl hypercrosslinked polymer having a microporous structure. The specific surface area of the hypercrosslinked polymer is 800-1800m 2 g -1 。
Preferably, the temperature of the amidation treatment is 60 to 300 ℃, and the time of the amidation reaction is 1 to 5 hours.
The invention provides a low dielectric constant hypercrosslinked polymer/polyimide composite film for high frequency prepared by the preparation method of the technical scheme, and the composite film can be applied in the fields of integrated circuits, microelectronics and insulating materials.
Mixing diaminodiphenyl ether, hexafluoro-isopropylene diphthalic anhydride and an aprotic solvent, carrying out polymerization reaction by a physical blending method to obtain a precursor polyamic acid solution, adding a super-crosslinked polymer, and carrying out physical blending to obtain a polyamic acid composite solution containing the super-crosslinked polymer; and coating the prepared polyamic acid composite solution on a glass plate, carrying out step-by-step heating, carrying out amidation reaction, and stripping from the glass plate to obtain the target composite film. The added hypercrosslinked polymer has high surface area and micropore structure, so that air can be introduced into the composite film, the dielectric constant of the composite film is further reduced, and the mechanical property and the thermal stability of the composite film are simultaneously maintained. The examples show that the dielectric constant of the polyimide composite film prepared by the invention is 1.6-2.5 in the range of 8.2-12.4 GHz. At the same time T 5％ The tensile strength and the tensile modulus are respectively 92MPa and 2.15GPa at 453 ℃, which shows that the composite film maintains excellent thermodynamic and mechanical properties.
Drawings
FIG. 1 is a Fourier infrared spectrum of films prepared in examples 1 and 2 of the present invention and comparative example 1;
FIG. 2 is a graph showing the dielectric constant versus frequency of the films prepared in examples 2 and 3 of the present invention and comparative example 1;
FIG. 3 is a TGA profile of films prepared according to examples 1, 2 of the present invention and comparative example 1;
FIG. 4 is a histogram of tensile strength of films prepared in example 1 of the present invention and comparative example 1;
FIG. 5 is a histogram of tensile modulus for films prepared in example 2 of the present invention and comparative example 1.
Detailed Description
The invention provides a preparation method of a low-dielectric-constant hypercrosslinked polymer/polyimide composite film used under high frequency, which comprises the following steps: mixing diaminodiphenyl ether, hexafluoro-isopropylene diphthalic anhydride and an aprotic solvent, carrying out polymerization reaction by a physical blending method to obtain a precursor polyamic acid solution, adding a super-crosslinked polymer into the precursor solution, and physically blending to obtain a polyamic acid composite solution containing the super-crosslinked polymer; and (3) coating the prepared polyamic acid composite solution on a glass plate by scraping, heating in a step mode, carrying out amidation reaction, peeling from the glass plate, and drying to obtain the target composite film.
In the present invention, the sources of the respective components are not particularly limited unless otherwise specified, and commercially available products known to those skilled in the art may be used.
In the invention, the mass ratio of the diaminodiphenyl ether to the hexafluoroisopropylidene diphthalic anhydride is 1: (2.3-2.5). The invention limits the mass ratio of the diaminodiphenyl ether and the hexafluoro-isopropylidene diphthalic anhydride in the range, can ensure that the diamine monomer and the dianhydride monomer fully react, adjusts the structure of the polyimide, and improves the performance and the stability of the polyimide composite film.
In the present invention, the hypercrosslinked polymer has a high specific surface area and a microporous structure, and the specific surface area thereof ranges from 800 to 1800m 2 g -1 。
The source of the hypercrosslinked polymer in the present invention is not particularly limited, and the surface area and pore size may be close to or larger than the above-mentioned ranges.
In the invention, the mass content of the hypercrosslinked polymer in the composite film is 5-20%, the dispersion of the hypercrosslinked polymer in the fluorinated polyimide matrix can be adjusted, the dielectric constant of the composite film is further reduced, and the composite film has excellent heat resistance and mechanical properties.
In the invention, the hexafluoroisopropylidene diphthalic anhydride is used as a dianhydride monomer, and the diaminodiphenyl ether is used as a diamine monomer to react to generate the polyimide. In the invention, the hexafluoro-isopropylidene diphthalic anhydride contains a biphenyl structure, so that the thermal stability and the mechanical property of the composite film can be improved, and the polarizability can be reduced by trifluoromethyl in a dianhydride monomer and ether bond in a diamine monomer, thereby reducing the dielectric constant.
In the present invention, the solvent preferably includes one of N, N-dimethylformamide, N-dimethylacetamide and N-methylpyrrolidone, more preferably N, N-dimethylacetamide.
In the invention, when the diamine monomer, the dianhydride monomer and the aprotic solvent are physically blended, the proportion of the diaminodiphenyl ether to the solvent is 1g (9-10) mL. The invention limits the mass concentration of the diaminodiphenyl ether in the range, is beneficial to the dispersion of the hypercrosslinked polymer, and obtains the composite film with good performance after subsequent high-temperature amidation.
In the present invention, the polymerization reaction is carried out in two steps, wherein the temperature of the primary polymerization reaction is preferably-5 to 5 ℃, and the time of the second polymerization reaction is preferably 5 to 10 hours, more preferably 5 to 8 hours at room temperature (25 ℃). In the present invention, the temperature and time of the polymerization reaction are limited to the above ranges, and the reaction can be more sufficiently performed.
After the polymerization reaction is completed, the present invention preferably performs bubble removal and compounding on the polymerization reaction product to obtain the polyamic acid compound solution.
In the present invention, the precursor polyamic acid solution needs to be defoamed after the polymerization reaction, and the defoaming is performed by standing at room temperature for 12 to 48 hours, preferably 24 hours.
In the present invention, the draw down to form a film is preferably carried out on a dry, clean glass plate. In the invention, the blade coating film formation is carried out on a film scraping machine.
After the polyamic acid composite solution is obtained, the polyamic acid composite solution is subjected to amidation treatment to obtain the polyimide composite film.
In the invention, the temperature of the amidation treatment is preferably 60-300 ℃, and the time of the amidation treatment is preferably 1-5 h; more preferably, the temperature is maintained at 60 ℃ for 40min, at 100 ℃ for 1h, at 200 ℃ for 1h and at 300 ℃ for 1h in sequence. In the present invention, the temperature increase rate during the amidation treatment is preferably 5 ℃/min. The temperature, time and heating rate of the amidation treatment are limited in the above ranges, so that the amidation reaction can be fully performed, and the polyimide composite film with good film forming property can be obtained.
The present invention does not require any special equipment for the amidation treatment, and equipment well known to those skilled in the art may be used. In the present invention, the amidation treatment is preferably performed in a muffle furnace.
After the amidation treatment is completed, the present invention preferably sequentially cools, strips and dries the amidation treated product to obtain the polyimide composite film.
In the present invention, the cooling is preferably natural cooling, and the end point of the cooling is preferably room temperature.
In the present invention, the drying is preferably air-blast drying, the drying temperature is preferably 60 ℃, and the drying time is preferably 1 to 3 hours, and more preferably 2 hours.
According to the invention, the hypercrosslinked polymer is added in the reaction process (in the precursor), so that the hypercrosslinked polymer can be more uniformly dispersed in the composite film, the mass content of the hypercrosslinked polymer is controlled, air is introduced under the condition of not causing agglomeration, the dielectric constant of the composite film is further reduced, the raw material composition and process parameters of each step are controlled, and the structure of polyimide is adjusted, so that the composite film has higher thermal stability and mechanical property.
The invention provides the low dielectric constant hypercrosslinked polymer/polyimide composite film for high frequency prepared by the preparation method of the technical scheme. In the present invention, the thickness of the polyimide composite film is preferably 15 to 25 μm.
The polyimide composite film prepared by the invention has lower dielectric constant and better thermal stability and mechanical property.
The invention also provides the application of the low dielectric constant hypercrosslinked polymer/polyimide composite film in the technical scheme in the fields of integrated circuits, microelectronics and insulating materials. The application of the low-dielectric-constant super-crosslinked polymer/polyimide composite film in the fields of integrated circuits, microelectronics and insulating materials is not particularly limited, and the technical scheme of the application of the polyimide composite film in the fields of integrated circuits, microelectronics and insulating materials, which is well known to a person skilled in the art, is adopted.
The technical solution of the present invention will be clearly and completely described below with reference to the embodiments of the present invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
Dissolving 2.0g of 4,4' -diaminodiphenyl ether in 18mL of N, N-dimethylformamide, and carrying out ultrasonic treatment for 30min until the solution is completely dissolved; then 4.6g of 4,4' - (hexafluoroisopropylene) diphthalic anhydride was slowly added in a low-temperature constant-temperature bath at a temperature of-5 ℃. Stirring for about 1h until rod climbing occurs, placing the mixed system in a room temperature environment, continuously stirring for 5h to obtain viscous polyamide acid solution, and standing for 24h at room temperature to remove bubbles. 2g of a polyamic acid solution was taken, and 0.03g of 4,4 '-bis (chloromethyl) -1,1' -biphenyl hypercrosslinked polymer (specific surface area 1800 m) was added 2 g -1 ) And performing magnetic stirring for 30min, and then performing ultrasonic dispersion for 2h to uniformly disperse the hypercrosslinked polymer in the polyamic acid solution to obtain the polyamic acid composite solution containing the hypercrosslinked polymer. Then the polyamic acid composite solution is cast on a dry and clean glass plate, a film with the thickness of about 300 mu m is formed by blade coating of a film scraping machine, the film is placed in a muffle furnace, thermal amidation is carried out in the temperature gradient of 60-300 ℃ (40 min at 60 ℃,1h at 100 ℃, 200 ℃ and 300 ℃ respectively, with the heating rate of 5 ℃/min), naturally cooling to room temperature, stripping the film, and then drying for 2h at 60 ℃ to obtain a polyimide composite film containing 5% of the hypercrosslinked polymer by mass, as 5% of HCP-FPI composite film, with a film thickness of 15 μm, a dielectric constant of 2.2-2.8 in the entire X band (8.2-12.4 GHz) 5％ 483 ℃ and a tensile strength of 92MPa.
Example 2
Dissolving 2.0g of 4,4' -diaminodiphenyl ether in 18mL of N, N-dimethylacetamide, and carrying out ultrasonic treatment for 30min until the solution is completely dissolved; then 4.6g of 4,4' - (hexafluoro-isopropylene) diphthalic anhydride is slowly added into an ice-water bath at the temperature of 0 ℃, the stirring is carried out for about 1 hour, when a rod climbing phenomenon occurs, the mixed system is placed in a room-temperature environment and is continuously stirred for 5 hours, a viscous polyamic acid solution is obtained, and the mixed system is kept stand for 24 hours at the room temperature to remove bubbles. 2g of a polyamic acid solution was taken, and 0.062g of 4,4 '-bis (chloromethyl) -1,1' -biphenyl hypercrosslinked polymer (specific surface area 1800 m) was added 2 g -1 ) And performing magnetic stirring for 30min, and then performing ultrasonic dispersion for 2h to uniformly disperse the hypercrosslinked polymer in the polyamic acid solution to obtain the polyamic acid composite solution containing the hypercrosslinked polymer. Then casting the polyamic acid composite solution on a dry and clean glass plate, carrying out blade coating by using a film scraping machine to form a film with the thickness of about 300 mu m, placing the film in a muffle furnace, carrying out thermal amidation in a temperature gradient of 60-300 ℃ (60 ℃, 40min,100 ℃, 200 ℃, 300 ℃ and 1h respectively, wherein the heating rate is 5 ℃/min), naturally cooling to room temperature, stripping the film, drying for 2h at 60 ℃ to obtain the polyimide composite film, marking as 10 percent, the HCP-FPI composite film with the thickness of 20 mu m, the dielectric constant of the whole X wave band (8.2-12.4 GHz) of 1.6-2.5, T 5％ At 453 ℃ and a tensile modulus of 2.15GPa.
Example 3
Dissolving 2.0g of 4,4' -diaminodiphenyl ether in 19mL of N, N-dimethylacetamide, and carrying out ultrasonic treatment for 30min until the solution is completely dissolved; then 4.8g of 4,4' - (hexafluoroisopropylene) diphthalic anhydride was slowly added to the ice-water bath at 0 ℃ and stirred for about 1 hour until the rod climbing phenomenon occurred, and the above mixed system was left to stir at room temperature for 5 hours to obtain a viscous polyamic acid solution, which was allowed to stand at room temperature for 24 hours to remove air bubbles. Get2g of a polyamic acid solution, 0.099g of 1, 4-bis (chloromethyl) phenyl hypercrosslinked polymer (specific surface area 800 m) 2 g -1 ) And magnetically stirring for 30min, and then performing ultrasonic dispersion for 2h to uniformly disperse the super-crosslinked polymer in the polyamic acid solution to obtain the polyamic acid composite solution containing the super-crosslinked polymer. Then casting the polyamic acid composite solution on a dry and clean glass plate, using a film scraping machine to scrape and coat the polyamic acid composite solution into a film with the film thickness of about 300 mu m, placing the film into a muffle furnace, performing thermal amidation in a temperature gradient of 60-300 ℃ (40min at 60 ℃, 200 ℃, 300 ℃ for 1h respectively, heating rate of 5 deg.C/min), naturally cooling to room temperature, peeling, and drying at 60 deg.C for 2h to obtain polyimide composite film, as 15% HCP-FPI composite film with thickness of 20 μm and dielectric constant of 1.7-2.5 in whole X band (8.2-12.4 GHz) 5％ The temperature was 444 ℃.
Example 4
Dissolving 2.0g of 4,4' -diaminodiphenyl ether in 20mL of N-methylpyrrolidone, and carrying out ultrasonic treatment for 30min till complete dissolution; then, 5.0g of 4,4' - (hexafluoroisopropylidene) diphthalic anhydride is slowly added into a low-temperature constant-temperature water bath at the temperature of 5 ℃, the stirring is carried out for about 1 hour, the mixed system is placed in a room-temperature environment to be continuously stirred for 5 hours when a pole climbing phenomenon occurs, a viscous polyamic acid solution is obtained, and the mixed system is kept stand for 24 hours at the room temperature to remove bubbles. 2g of a polyamic acid solution was taken, and 0.140g of 4,4 '-bis (chloromethyl) -1,1' -biphenyl hypercrosslinked polymer (specific surface area 1800 m) was added 2 g -1 ) And magnetically stirring for 30min, and then performing ultrasonic dispersion for 2h to uniformly disperse the super-crosslinked polymer in the polyamic acid solution to obtain the polyamic acid composite solution containing the super-crosslinked polymer. Then casting the polyamic acid composite solution on a dry and clean glass plate, carrying out blade coating by using a film scraping machine to form a film with the thickness of about 300 mu m, placing the film in a muffle furnace, carrying out thermal amidation in a temperature gradient of 60-300 ℃ (60 ℃, 40min,100 ℃, 200 ℃, 300 ℃ and 1h respectively, the heating rate is 5 ℃/min), naturally cooling to room temperature, stripping the film, then drying for 2h at 60 ℃ to obtain the polyimide composite film, marking as 20 percent HCP-FPI composite film with the thickness of 25 mu m, the dielectric constant of the whole X wave band (8.2-12.4 GHz) is 2.2-3.0, T is T 5％ It was 425 ℃.
Comparative example 1
In comparative example 1, no hypercrosslinked polymer was added, and the other parameters were the same as in example 1, and a polyimide film, designated as an FPI film, having a film thickness of 20 μm and a dielectric constant of 2.3 to 3.0 at 8.2 to 12.4GHz was obtained, indicating that the dielectric constant at high frequencies can be significantly reduced by uniformly compounding the hypercrosslinked polymer.
Fourier transform Infrared Spectroscopy testing of films prepared in examples 1, 2 and comparative example 1 Fourier transform Infrared Spectroscopy was performed by cutting the prepared films into 30mm by 30mm pieces and scanning the pieces in a range of 2000 to 500cm -1 The results are shown in FIG. 1. As can be seen in FIG. 1, the four IR absorption peaks are at 1783cm -1 (asymmetric stretching vibration of C = O double bond of imide ring), 1716cm -1 (imide Ring C = O double bond symmetric stretching vibration), 1372cm -1 (vibration of imide ring C-N bond stretching) 720cm -1 (bending vibration in an imide ring surface), the four IR absorption peaks jointly form a characteristic peak of PI, and the polyimide film is successfully prepared by adopting the preparation method.
The dielectric properties of the films prepared in examples 3 and 4 and comparative example 1 were measured by a vector network analyzer in a frequency range of 8.2GHz to 12.4GHz, and the results are shown in FIG. 2. As can be seen from FIG. 2, the dielectric constants of the composite films prepared by the invention are all low, and when the doping amount of the hypercrosslinked polymer is 10wt%, the dielectric constant of the composite film can be reduced to 1.6-2.5 in the whole X wave band (8.2-12.4 GHz); the dielectric constant of the composite film can be lowered only when the content of the hypercrosslinked polymer is within the range defined by the present invention.
The TGA curves of the films prepared in examples 1 and 2 and comparative example 1 were tested, and thermogravimetric analysis (TGA) of the composite film was performed using TGA/DSC 2 in air at a heating rate of 10 ℃/min, and the results are shown in fig. 3. 5% thermal decomposition temperature (T) of the composite film prepared by the invention 5％ ) Are all higher, when the doping amount of the super-crosslinked polymer is 10wt%, the T of the composite film is 5％ Can still be maintained at 453 ℃; t of the composite film is increased along with the increase of the doping amount 5％ Slightly decreased and still kept above 425 ℃.
The films prepared in examples 1, 2 and comparative example 1 were tested for mechanical properties and measured using a universal tester at a strain rate of 2 mm/min. The sample length and width were 25mm and 5mm, respectively. Five measurements were averaged for each sample. The results are shown in FIGS. 4 and 5. The composite film prepared by the invention has good overall mechanical property, and when the doping amount of the hypercrosslinked polymer is 5wt%, the tensile strength of the composite film is 92MPa; when the doping amount of the hypercrosslinked polymer is 10wt%, the tensile modulus of the composite film is 2.15GPa; good mechanical properties can only be maintained when the content of the hypercrosslinked polymer is within the range defined by the present invention.
In conclusion, the composite film prepared by the invention has lower dielectric constant and better thermal stability and mechanical property under high frequency.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and amendments can be made without departing from the principle of the present invention, and these modifications and amendments should also be considered as the protection scope of the present invention.
Claims (10)
1. A low dielectric constant hypercrosslinked polymer/polyimide composite film used under high frequency and its preparation method, characterized by that, including the following steps:
(1) Mixing diaminodiphenyl ether, hexafluoro-isopropylene diphthalic anhydride and aprotic solvent by a physical blending method, and carrying out polymerization reaction to obtain a precursor polyamic acid solution;
(2) Adding a super cross-linked polymer into a precursor polyamic acid solution, and physically blending to obtain a polyamic acid composite solution containing the super cross-linked polymer;
(3) And (3) coating the polyamide acid composite solution containing the super cross-linked polymer on a glass plate, heating in a stepped manner, carrying out amidation reaction, peeling from the glass plate, and drying to obtain the super cross-linked polymer/polyimide composite film with low dielectric constant under high frequency.
2. The method according to claim 1, wherein the mass ratio of diaminodiphenyl ether to hexafluoroisopropylidene diphthalic anhydride in step (1) is 1: (2.3-2.5).
3. The method according to claim 1, wherein the aprotic solvent in step (1) is one of N, N-dimethylformamide, N-dimethylacetamide and N-methylpyrrolidone.
4. The method according to claim 1, wherein when the diaminodiphenyl ether, the hexafluoroisopropylidene diphthalic anhydride and the aprotic solvent are physically blended in step (1), the ratio of the diaminodiphenyl ether to the solvent is 1g (9-10) mL.
5. The method according to claim 1, wherein the polymerization reaction of diaminodiphenyl ether and hexafluoroisopropylidene diphthalic anhydride in step (1) is carried out at-5 to 5 ℃ for 1 to 2 hours and then at room temperature for 4 to 8 hours.
6. The preparation method according to claim 1, wherein the mass content of the hypercrosslinked polymer in the composite membrane in the step (2) is 5-20%.
7. The method of claim 1, wherein the physical blending method is one or more of mechanical stirring, magnetic stirring, and ultrasonic dispersion.
8. The process according to claim 1, wherein the temperature of the amidation reaction in the step (3) is 60 to 300 ℃, and the time of the amidation reaction is 1 to 5 hours.
9. The method according to claim 1, wherein the hypercrosslinked polymer is one of a 4,4 '-bis (chloromethyl) -1,1' -biphenyl hypercrosslinked polymer and a 1, 4-bis (chloromethyl) phenyl hypercrosslinked polymer having a microporous structure.
10. The polyimide composite film with low dielectric constant under high frequency prepared by the method according to the claims 1 to 9 can be applied to the fields of integrated circuits, microelectronics and insulating materials.
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| LI WEIXIN等: "Hyper cross‐linked polymers containing amino group functionalized polyimide mixed matrix membranes for gas separation", JOURNAL OF APPLIED POLYMER SCIENCE, vol. 139, no. 20 * |
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