CN112851996B - Low-dielectric-constant cross-linked fluorine-containing poly (arylene ether nitrile) film and preparation method and application thereof - Google Patents

Low-dielectric-constant cross-linked fluorine-containing poly (arylene ether nitrile) film and preparation method and application thereof Download PDF

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CN112851996B
CN112851996B CN202110309603.XA CN202110309603A CN112851996B CN 112851996 B CN112851996 B CN 112851996B CN 202110309603 A CN202110309603 A CN 202110309603A CN 112851996 B CN112851996 B CN 112851996B
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黄宇敏
刘宸辰
曾子秋
王登善
刘孝波
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University of Electronic Science and Technology of China
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Abstract

The invention discloses a low-dielectric-constant cross-linked fluorine-containing poly (arylene ether nitrile) film and a preparation method and application thereof, belonging to the technical field of polymer synthesis. The crosslinkable polyarylether nitrile film is prepared by dissolving the crosslinkable polyarylether nitrile I and a catalyst in a polar solvent and casting into a film; after drying and forming, carrying out high-temperature heat treatment; and after cooling, soaking the film in water, and drying to obtain the low-dielectric-constant cross-linked fluorine-containing poly (arylene ether nitrile) film. The invention takes crosslinkable fluorine-containing poly (arylene ether nitrile) as a raw material, and leads polar cyano groups on the main chain of the poly (arylene ether nitrile) to have crosslinking reaction through crosslinking reaction to form a compact network structure, thereby obtaining the low-dielectric fluorine-containing poly (arylene ether nitrile) film which has more excellent heat resistance and strength. The preparation method is simple and easy for industrial operation, and the obtained low dielectric film can be applied to the fields of integrated circuits, 5g communication antenna materials or flexible copper clad plates and the like.

Description

Low-dielectric-constant cross-linked fluorine-containing poly (arylene ether nitrile) film and preparation method and application thereof
Technical Field
The invention belongs to the technical field of polymer synthesis, and particularly relates to a low-dielectric-constant cross-linked fluorine-containing poly (arylene ether nitrile) film, and a preparation method and application thereof.
Background
With the rapid development of electronic information technology, electronic information products are moving toward high frequency, high speed, multi-functionalization and miniaturizationThe direction of thin and light weight is developed. Meanwhile, the development of very large scale integrated circuits has led to the increasing of interconnection density in chips, the decreasing of width and spacing of interconnection lines, and the more and more obvious parasitic effect generated by interconnection resistance (R) and capacitance (C), and further to the severe delay of signals. The use of low dielectric constant packaging materials that are less affected by the transmitted signal is a major approach to this problem. Therefore, for low dielectric constant (k) with good performance<3) There is a pressing need for materials. Compared with the conventional low dielectric inorganic substance (such as SiO)2) The low dielectric organic polymer has the advantages of diversified molecular design, good processing performance and the like, thereby attracting the interest of the majority of researchers.
The poly (arylene ether nitrile) serving as a novel special high polymer material has the excellent characteristics of high thermal stability, flame retardance, radiation resistance, corrosion resistance, good dimensional stability, high mechanical strength and the like, and is widely applied to the fields of aerospace, mechano-electronics, automobile manufacturing, chemical engineering petroleum, medical health and the like. Although the polyarylether nitrile has excellent comprehensive performance, the dielectric constant of the traditional polyarylether nitrile material is generally about 4 due to the existence of polar cyano groups on the main chain, and if the polyarylether nitrile material is used as a packaging material in the field of microelectronics, the dielectric constant of the polyarylether nitrile material needs to be further reduced. Therefore, the development of low dielectric constant poly (arylene ether nitrile) materials is of great significance.
Currently, supercritical CO is commonly used in the industry2Foaming techniques or the introduction of specific blowing agents to reduce the dielectric constant, mainly introduce pores into the polymer film. However, this method has the obvious disadvantages that the size of the micropores is difficult to control, and the existence of the micropores often causes the mechanical properties of the film to be poor, and the water absorption to be increased, thereby affecting the overall performance of the film.
Disclosure of Invention
Aiming at the problems in the prior art, the invention provides a low-dielectric-constant crosslinking type fluorine-containing poly (arylene ether nitrile) film which has the advantages of high heat resistance, high strength and the like.
The invention firstly provides a preparation method of a low-dielectric-constant crosslinking type fluorine-containing polyaryl ether nitrile film, which comprises the following steps:
Figure BDA0002989002510000011
dissolving the crosslinkable poly (arylene ether nitrile I) and a catalyst in a polar solvent, and preparing a crosslinkable poly (arylene ether nitrile) film by a tape casting film-forming method; after the obtained crosslinkable poly (arylene ether nitrile) film is subjected to gradient heating, drying and forming, performing high-temperature heat treatment at 300-360 ℃; then cooling, soaking the film in water, and finally drying to obtain the low-dielectric-constant cross-linked fluorine-containing poly (arylene ether nitrile) film;
wherein m is more than 0 and less than or equal to 1, n is 1-m, -Ar-is derived from dihydric phenol in the crosslinkable polyarylether nitrile I;
wherein the catalyst is at least one of Lewis acid, protonic acid or acidic oxide.
In the preparation method of the low-dielectric-constant cross-linked fluorine-containing polyarylethernitrile film, the dihydric phenol comprises the following substituted or unsubstituted structure:
Figure BDA0002989002510000021
wherein X is H or F; the substituted substituent is C1-C6 alkyl, 6-10-membered aryl or 5-10-membered heteroaryl.
In the preparation method of the low-dielectric-constant cross-linked fluorine-containing polyaryl ether nitrile film, the mass ratio of the catalyst to the cross-linkable polyaryl ether nitrile I is 0.5-5%.
Preferably, in the preparation method of the low-dielectric-constant cross-linked fluorine-containing polyarylene ether nitrile film, the lewis acid is AlCl3、FeCl3、BeCl2、SnCl4、CrCl3、BiCl3、LaCl3、BF3Or ZnCl2At least one of (a).
Preferably, in the method for preparing the low-dielectric-constant crosslinked fluorine-containing polyarylene ether nitrile film, the protonic acid is H2SO4、H3PO4BingyiAt least one of an acid, trifluoromethanesulfonic acid, p-toluenesulfonic acid, propionic acid, phosphotungstic acid, or HF.
Preferably, in the method for preparing a low dielectric constant crosslinked polyarylene ether nitrile film, the acidic oxide is Fe2O3、TiO2、WO3、Sb2O3At least one of natural zeolite, quartz or diatomaceous earth.
In the preparation method of the low dielectric constant cross-linked fluorine-containing polyarylethernitrile film, the polar solvent is at least one of diphenylsulfone, dimethyl sulfoxide, sulfolane, N-methylpyrrolidone, N-dimethylformamide or N, N-dimethylacetamide.
In the preparation method of the low-dielectric-constant cross-linked fluorine-containing polyaryl ether nitrile film, the concentration of the cross-linked polyaryl ether nitrile I subsystem is 0.05-0.15 g/mL.
In the preparation method of the low-dielectric-constant cross-linked fluorine-containing polyaryl ether nitrile film, the specific operation of gradient temperature rise is as follows: firstly drying at 80 +/-5 ℃ for 1-2 h, then drying at 100 +/-5 ℃ for 1-2 h, then drying at 120 +/-5 ℃ for 1-2 h, then drying at 160 +/-10 ℃ for 1-2 h, and finally drying at 200 +/-10 ℃ for 1-2 h.
In the preparation method of the low-dielectric-constant cross-linking type fluorine-containing polyaryl ether nitrile film, the high-temperature heat treatment time is 2-6 h.
In the preparation method of the low-dielectric-constant cross-linked fluorine-containing poly (arylene ether nitrile) film, the soaking temperature is 40-60 ℃.
In the preparation method of the low-dielectric-constant cross-linked fluorine-containing poly (arylene ether nitrile) film, the soaking time is 8-24 hours.
The invention also provides the low-dielectric-constant crosslinking type fluorine-containing polyaryl ether nitrile film prepared by the method.
The low-dielectric-constant crosslinking type fluorine-containing poly (arylene ether nitrile) film provided by the invention has excellent performance, and T is5％A thermal decomposition temperature of 500 ℃ or higher, a tensile strength of 65MPa or higher, a dielectric constant of 2.00 to 2.90 at 1kHz, a dielectric loss of 0.003 to 0.01, and a thicknessThe degree is 10 um-30 um.
Therefore, the low-dielectric-constant cross-linked fluorine-containing polyaryl ether nitrile film provided by the invention can be widely applied to the fields of integrated circuits, 5g communication antenna materials or flexible copper clad plates and the like.
The invention has the beneficial effects that:
the invention takes crosslinkable fluorine-containing poly (arylene ether nitrile) as a raw material, and leads polar cyano groups on the main chain of the poly (arylene ether nitrile) to have crosslinking reaction through crosslinking reaction to form a compact network structure, thereby obtaining the low-dielectric fluorine-containing poly (arylene ether nitrile) film; meanwhile, due to the crosslinking reaction, the obtained poly (arylene ether nitrile) film has more excellent heat resistance and strength. The preparation method is simple and easy for industrial operation, and the prepared low dielectric film can be applied to the fields of integrated circuits, 5g communication antenna materials or flexible copper clad plates and the like.
Drawings
Fig. 1 is a schematic diagram of a cross-linking type polyarylene ether nitrile film prepared by subjecting polyarylene ether nitrile to a cross-linking reaction according to the present invention.
Detailed Description
Specifically, the preparation method of the low-dielectric-constant cross-linked fluorine-containing polyaryl ether nitrile film comprises the following steps:
Figure BDA0002989002510000031
dissolving the crosslinkable poly (arylene ether nitrile I) and a catalyst in a polar solvent, and preparing a crosslinkable poly (arylene ether nitrile) film by a tape casting film-forming method; after the obtained crosslinkable polyarylethernitrile film is subjected to gradient heating, drying and molding, performing high-temperature heat treatment at 300-360 ℃; then cooling, soaking the film in water, and finally drying to obtain the low-dielectric-constant cross-linked fluorine-containing poly (arylene ether nitrile) film;
wherein in the crosslinkable polyarylether nitrile I, m is more than 0 and less than or equal to 1, n is 1-m, -Ar-is derived from dihydric phenol:
wherein the catalyst is at least one of Lewis acid, protonic acid or acidic oxide.
The crosslinkable polyarylene ether nitriles I of the invention can be prepared according to the following equation:
Figure BDA0002989002510000041
according to the invention, bisphenol AF is used as one of reaction monomers for synthesizing raw materials, and fluorine atoms are introduced into the raw material crosslinkable poly (arylene ether nitrile I), so that the polymer has a lower dielectric constant, and the electronic polarization is effectively reduced; then, through a crosslinking reaction, a polar cyano group on the main chain of the poly (arylene ether nitrile) is subjected to a crosslinking reaction to generate a triazine ring structure to form a compact network structure, so that the low-dielectric fluorine-containing poly (arylene ether nitrile) film is obtained; meanwhile, due to the introduction of a crosslinking reaction, the obtained poly (arylene ether nitrile) film has more excellent heat resistance.
According to the formula for synthesizing the crosslinkable polyarylene ether nitrile I, the-Ar-in the crosslinkable polyarylene ether nitrile I is derived from dihydric phenol, and the dihydric phenol can be selected from dihydric phenols common in the art, which specifically includes the following substituted or unsubstituted structures:
Figure BDA0002989002510000042
wherein X is H or F; the substituted substituent is C1-C6 alkyl, 6-10-membered aryl or 5-10-membered heteroaryl.
In the method of the invention, at least one of Lewis acid, protonic acid or acidic oxide can be used as the crosslinking reaction catalyst; wherein the Lewis acid can adopt AlCl3、FeCl3、BeCl2、SnCl4、CrCl3、BiCl3、LaCl3、BF3Or ZnCl2At least one of; the protonic acid can be H2SO4、H3PO4At least one of glacial acetic acid, trifluoromethanesulfonic acid, p-toluenesulfonic acid, propionic acid, phosphotungstic acid, or HF; the acidic oxide can adopt Fe2O3、TiO2、WO3、Sb2O3At least one of natural zeolite, quartz or diatomaceous earth. Through tests, theThe adding amount of the catalyst is 0.5-5% of the mass of the raw material crosslinkable poly (arylene ether nitrile I).
In the method of the present invention, the polar solvent may be at least one of diphenyl sulfone, dimethyl sulfoxide, sulfolane, N-methylpyrrolidone, N-dimethylformamide or N, N-dimethylacetamide, so as to facilitate the dissolution of the raw material crosslinkable poly (arylene ether nitrile I) and facilitate the subsequent removal of the solvent by gradient temperature rise.
In the method, in order to enable the film to have excellent performance (especially dielectric performance), the concentration of the crosslinkable poly (arylene ether nitrile) I subsystem needs to be controlled to be 0.05-0.15 g/mL, so that the film has proper thickness; too high concentration can cause the film to be too thick, and the inside of the film is easy to have defects; the concentration is low, and the film is difficult to peel from the glass plate.
In the method, the specific operation of gradient temperature rise is as follows: firstly drying at 80 +/-5 ℃ for 1-2 h, then drying at 100 +/-5 ℃ for 1-2 h, then drying at 120 +/-5 ℃ for 1-2 h, then drying at 160 +/-10 ℃ for 1-2 h, and finally drying at 200 +/-10 ℃ for 1-2 h; the solvent can be fully removed by adopting gradient heating, more importantly, the quality of the film is improved by adopting the gradient heating, and the quality of the film has influence on the performance of the film; if a rapid heating means is adopted, the solvent is evaporated too fast, and the problems of unevenness, uneven thickness, internal defects and the like of the film are easy to occur.
In the method, the influence of the temperature and the time of high-temperature heat treatment on the performance of the film is large. Tests show that the crosslinking reaction can also occur at the temperature below 300 ℃ (above 280 ℃), but the reaction is slow, so that the crosslinking time is greatly increased; if the temperature is too high, excessive crosslinking can occur, so that the film is fragile and inflexible; in addition, too short a heat treatment time may result in incomplete crosslinking and too long a heat treatment time may result in a brittle film. Therefore, the temperature of the high-temperature heat treatment is required to be controlled to be 300-360 ℃ and the time is 2-6 h.
Generally, a carrier (such as a glass plate) is needed for casting film formation, so that after the crosslinking reaction is finished and cooled, the film needs to be soaked in water to naturally fall off from the carrier; meanwhile, if a small amount of metal catalyst remains in the film, the dielectric loss is increased; therefore, in the method, the membrane needs to be soaked in warm water at the temperature of 40-60 ℃ for 8-24 hours, so that the membrane is prevented from being damaged by utilizing the natural falling of the membrane, and the catalyst is removed as far as possible.
The invention firstly introduces fluorine-containing groups into crosslinkable poly (arylene ether nitrile I), and then leads polar cyano groups on the main chain of the poly (arylene ether nitrile) to react through crosslinking reaction, thereby obtaining the poly (arylene ether nitrile) film with low dielectric, medium frequency and stable medium temperature, and T thereof5％The thermal decomposition temperature is more than 500 ℃, the tensile strength is more than 65MPa, the dielectric constant of the material under 1kHz is 2.00-2.90, the dielectric loss is 0.003-0.01, and the thickness is 10-30 um.
Therefore, the low-dielectric-constant cross-linked fluorine-containing polyaryl ether nitrile film provided by the invention can be widely applied to the fields of integrated circuits, 5g communication antenna materials or flexible copper clad plates and the like.
The present invention is further illustrated by the following examples, without thereby limiting the scope of the invention to the examples described.
Example 1
Figure BDA0002989002510000051
2g of crosslinkable poly (arylene ether nitrile) I-a and 0.01g of zinc chloride are dissolved in 20mL of N-methyl pyrrolidone, a crosslinkable poly (arylene ether nitrile) film is prepared by a tape casting film forming method, and in order to fully remove the solvent, the program temperature of an oven is set to be 80-2 h, 100-2 h, 120-2 h, 160-2 h and 200-2 h in sequence.
Putting the dried and formed film into a high-temperature oven for heat treatment, and carrying out high-temperature heat treatment at 320 ℃ for 4 hours; and then naturally cooling the sample film to room temperature, soaking the sample film in warm water at 60 ℃ for 12h, stripping the film from a glass plate, simultaneously completely removing the catalyst, and then drying to obtain the cross-linked poly (arylene ether nitrile) film.
The thickness of the cross-linking type poly (arylene ether nitrile) film prepared by the steps is 18um, and the performance test is as follows: t is5％The thermal decomposition temperature is 520 ℃, and the tensile strength is 65 MPa. While having a dielectric constant at 1kHz of2.87, dielectric loss 0.009.
Example 2
Figure BDA0002989002510000061
2g of crosslinkable poly (arylene ether nitrile) I-a and 0.02g of ferric trichloride are dissolved in 20mL of N-methyl pyrrolidone, and a crosslinkable poly (arylene ether nitrile) film is prepared by a tape casting film forming method, wherein in order to fully remove the solvent, the program temperature of an oven is set to be 80-2 h, 100-2 h, 120-2 h, 160-2 h and 200-2 h in sequence.
Putting the dried and formed film into a high-temperature oven for heat treatment, and carrying out heat treatment at the high-temperature of 360 ℃ for 2 h; and then naturally cooling the sample film to room temperature, soaking the sample film in warm water at 60 ℃ for 12h, stripping the film from a glass plate, simultaneously completely removing the catalyst, and then drying to obtain the cross-linked poly (arylene ether nitrile) film.
The thickness of the cross-linking type poly (arylene ether nitrile) film prepared by the steps is 22um, and the performance test is as follows: t is5％The thermal decomposition temperature is 528 ℃, and the tensile strength is 83 MPa. Meanwhile, the dielectric constant of the material at 1kHz is 2.62, and the dielectric loss is 0.006.
Example 3
Figure BDA0002989002510000062
2g of crosslinkable poly (arylene ether nitrile) I-b and 0.02g of ferric trichloride are dissolved in 20mL of N-methyl pyrrolidone, a crosslinkable poly (arylene ether nitrile) film is prepared by a tape casting film forming method, and in order to fully remove the solvent, the program temperature of an oven is set to be 80-2 h, 100-2 h, 120-2 h, 160-2 h and 200-2 h in sequence.
Putting the dried and formed film into a high-temperature oven for heat treatment, and carrying out heat treatment at the high-temperature of 360 ℃ for 2 h; and then naturally cooling the sample film to room temperature, soaking the sample film in warm water at 60 ℃ for 12h, stripping the film from a glass plate, simultaneously completely removing the catalyst, and then drying to obtain the cross-linked poly (arylene ether nitrile) film.
The thickness of the cross-linking type poly (arylene ether nitrile) film prepared by the steps is 28um, and the performance test is as follows: t is5％The thermal decomposition temperature is 521 ℃, and the tensile strength is 81 MPa. Meanwhile, the dielectric constant of the material at 1kHz is 2.65, and the dielectric loss is 0.007.
Example 4
Figure BDA0002989002510000063
1.5g of crosslinkable poly (arylene ether nitrile) I-c and 0.02g of zinc chloride are dissolved in 20mL of N-methyl pyrrolidone, a crosslinkable poly (arylene ether nitrile) film is prepared by a tape casting film forming method, and in order to fully remove the solvent, the program temperature of an oven is set to be 80-2 h, 100-2 h, 120-2 h, 160-2 h and 200-2 h in sequence.
Putting the dried and formed film into a high-temperature oven for heat treatment, and carrying out high-temperature heat treatment at 340 ℃ for 4 h; and then naturally cooling the sample film to room temperature, soaking the sample film in warm water at 60 ℃ for 12h, stripping the film from a glass plate, simultaneously completely removing the catalyst, and then drying to obtain the cross-linked poly (arylene ether nitrile) film.
The thickness of the cross-linking type poly (arylene ether nitrile) film prepared by the steps is 30um, and the performance test is as follows: t is5％The thermal decomposition temperature is 535 ℃, and the tensile strength is 92 MPa. Meanwhile, the dielectric constant of the material at 1kHz is 2.76, and the dielectric loss is 0.009.
Example 5
Figure BDA0002989002510000071
1.5g of crosslinkable poly (arylene ether nitrile) I-d and 0.02g of ferric trichloride are dissolved in 20mL of N-methyl pyrrolidone, a crosslinkable poly (arylene ether nitrile) film is prepared by a tape casting film forming method, and in order to fully remove the solvent, the program temperature of an oven is set to be 80-2 h, 100-2 h, 120-2 h, 160-2 h and 200-2 h in sequence.
Putting the dried and formed film into a high-temperature oven for heat treatment, and carrying out high-temperature heat treatment at 320 ℃ for 4 hours; and then naturally cooling the sample film to room temperature, soaking the sample film in warm water at 60 ℃ for 12h, stripping the film from a glass plate, simultaneously completely removing the catalyst, and then drying to obtain the cross-linked poly (arylene ether nitrile) film.
The thickness of the cross-linking type poly (arylene ether nitrile) film prepared by the steps is 25um, and the performance test is as follows: t is5％The thermal decomposition temperature is 552 ℃, and the tensile strength is 96 MPa. Meanwhile, the dielectric constant of the material at 1kHz is 2.80, and the dielectric loss is 0.008.
Example 6
Figure BDA0002989002510000072
1.5g of crosslinkable poly (arylene ether nitrile) I-e and 0.01g of zinc chloride are dissolved in 20mL of N-methyl pyrrolidone, a casting film forming method is adopted to prepare the crosslinkable poly (arylene ether nitrile) film, and in order to fully remove the solvent, the program temperature of an oven is set to be 80-2 h, 100-2 h, 120-2 h, 160-2 h and 200-2 h in sequence.
Putting the dried and formed film into a high-temperature oven for heat treatment, and carrying out high-temperature heat treatment at 340 ℃ for 4 h; and then naturally cooling the sample film to room temperature, soaking the sample film in warm water at 60 ℃ for 12 hours, stripping the film from a glass plate, simultaneously completely removing the catalyst, and then drying to obtain the cross-linked poly (arylene ether nitrile) film.
The cross-linking type poly (arylene ether nitrile) film prepared by the steps has the thickness of 20um, and the performance test is as follows: t is5％The thermal decomposition temperature is 525 ℃ and the tensile strength is 88 MPa. Meanwhile, the dielectric constant of the material at 1kHz is 2.75, and the dielectric loss is 0.008.

Claims (10)

1. The preparation method of the low dielectric constant crosslinking type fluorine-containing polyaryl ether nitrile film is characterized by comprising the following steps: the method comprises the following steps:
Figure FDA0003568653630000011
dissolving the crosslinkable poly (arylene ether nitrile I) and a catalyst in a polar solvent, and preparing a crosslinkable poly (arylene ether nitrile) film by a tape casting film-forming method; after the obtained crosslinkable poly (arylene ether nitrile) film is subjected to gradient heating, drying and forming, performing high-temperature heat treatment at 300-360 ℃; then cooling, soaking the film in water, and finally drying to obtain the low-dielectric-constant cross-linked fluorine-containing poly (arylene ether nitrile) film;
wherein m is more than 0 and less than or equal to 1, n is 1-m, -Ar-is derived from dihydric phenol in the crosslinkable polyarylether nitrile I;
wherein the catalyst is at least one of Lewis acid, protonic acid or acidic oxide;
t of the low dielectric constant crosslinking type fluorine-containing poly (arylene ether nitrile) film5％The thermal decomposition temperature is more than 500 ℃, the tensile strength is more than 65MPa, the dielectric constant of the material under 1kHz is 2.00-2.90, the dielectric loss is 0.003-0.01, and the thickness is 10-30 um.
2. The method for preparing a low dielectric constant crosslinked type fluorine-containing polyarylene ether nitrile film according to claim 1, wherein: the dihydric phenol comprises the following substituted or unsubstituted structure:
Figure FDA0003568653630000012
wherein X is H or F; the substituted substituent is C1-C6 alkyl, 6-10-membered aryl or 5-10-membered heteroaryl.
3. The method for preparing a low dielectric constant crosslinked type fluorine-containing polyarylene ether nitrile film according to claim 1, wherein: the mass ratio of the catalyst to the crosslinkable polyarylether nitrile I is 0.5-5%.
4. The method for preparing a low dielectric constant crosslinked type fluorine-containing polyarylene ether nitrile film according to claim 1, wherein: at least one of the following is satisfied:
the Lewis acid is AlCl3、FeCl3、BeCl2、SnCl4、CrCl3、BiCl3、LaCl3、BF3Or ZnCl2At least one of;
the protonic acid is H2SO4、H3PO4At least one of glacial acetic acid, trifluoromethanesulfonic acid, p-toluenesulfonic acid, propionic acid, phosphotungstic acid, or HF;
the acidic oxide is Fe2O3、TiO2、WO3、Sb2O3At least one of natural zeolite, quartz or diatomaceous earth.
5. The method for preparing a low dielectric constant crosslinked type fluorine-containing polyarylene ether nitrile film according to claim 1, wherein: at least one of the following is satisfied:
the polar solvent is at least one of diphenyl sulfone, dimethyl sulfoxide, sulfolane, N-methyl pyrrolidone, N-dimethylformamide or N, N-dimethylacetamide;
the concentration in the crosslinkable polyarylether nitrile I subsystem is 0.05-0.15 g/mL.
6. The method for preparing a low dielectric constant crosslinked type fluorine-containing polyarylene ether nitrile film according to claim 1, wherein: at least one of the following is satisfied:
the specific operation of gradient temperature rise is as follows: firstly drying at 80 +/-5 ℃ for 1-2 h, then drying at 100 +/-5 ℃ for 1-2 h, then drying at 120 +/-5 ℃ for 1-2 h, then drying at 160 +/-10 ℃ for 1-2 h, and finally drying at 200 +/-10 ℃ for 1-2 h;
the time of the high-temperature heat treatment is 2-6 h.
7. The method for preparing a low dielectric constant crosslinked type fluorine-containing polyarylene ether nitrile film according to any one of claims 1 to 6, wherein: the soaking temperature is 40-60 ℃; the soaking time is 8-24 h.
8. The low-dielectric-constant crosslinked fluorine-containing polyarylene ether nitrile film obtained by the production method according to any one of claims 1 to 7.
9. The low-dielectric-constant crosslinked fluorine-containing polyarylene ether nitrile film according to claim 8, wherein: t of it5％The thermal decomposition temperature is more than 500 ℃, the tensile strength is more than 65MPa, the dielectric constant of the material under 1kHz is 2.00-2.90, the dielectric loss is 0.003-0.01, and the thickness is 10-30 um.
10. The application of the low-dielectric-constant cross-linked fluorine-containing polyaryl ether nitrile film obtained by the preparation method of any one of claims 1 to 7 in integrated circuits, 5g communication antenna materials or flexible copper clad plates.
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