Low dielectric poly (arylene ether nitrile) composite material and preparation method thereof

Abstract

The present invention relates to a low-dielectric poly (arylene ether nitrile) composite material and a preparation method thereof, and belongs to the technical field of polymer dielectric materials. The technical problem solved by the present invention is to provide a preparation method for a low-dielectric poly (arylene ether nitrile) composite material with good process controllability. The method introduces hollow glass microspheres and performs organic modification treatment on the surface to obtain a functional filler with a core-shell structure; a trifluoromethyl group with a strong electronegativity is introduced into the poly (arylene ether nitrile) to prepare a poly (arylene ether nitrile) composite material. The material not only has a low dielectric constant and dielectric loss, but also exhibits good thermodynamic properties, and the compatibility and dispersibility between the filler and the matrix resin are good. The prepared composite material has better mechanical properties and can be used in the field of 5G communication technology, further expanding its use in the field of electronic materials. The method of the present invention is simple and controllable, and is suitable for large-scale industrial production.

Description

Technical Field

[0001] The invention relates to a low-dielectric polyarylethernitrile composite material and a preparation method thereof, belonging to the technical field of polymer dielectric materials. Background Art

[0002] The dielectric constant (ε) of early medium and low dielectric materials was 3.3<ε<20, while the dielectric constant of current low dielectric materials is 2.2<ε<3.3. With the maturity of 5G communication technology, the requirements for low dielectric materials are getting higher and higher, requiring a dielectric constant less than 2.2 so that they can be used in the field of ultra-low dielectric constant. As a special engineering plastic, poly (arylene ether nitrile) has a dielectric constant of about 3.3 at room temperature and high frequency (1GHz) environment, and a dielectric loss of about 4×10 -3 , cannot meet the requirements of low dielectric materials and needs further improvement.

[0003] Patent CN109776847A discloses a low-dielectric poly(arylene ether nitrile) foam material with a bimodal pore structure, as well as its preparation method and uses. Using nano-SiO2 as a heterogeneous nucleating agent, the bimodal PEN foam is produced through intermittent supercritical fluid foaming, utilizing both homogeneous nucleation of the PEN bulk and heterogeneous nucleation of nano-SiO2 particles. Large pores reduce the material's dielectric constant, while small pores provide improved mechanical properties.

[0004] Patent CN110105575A discloses a low-dielectric-constant poly(arylene ether nitrile) and its preparation method. The chemical structure of this poly(arylene ether nitrile) contains low-polarity trifluoromethyl and sulfone groups, which can reduce the dielectric constant of the system. Furthermore, the poly(arylene ether nitrile) is pore-formed by a porogen, resulting in a large number of pores within the low-dielectric-constant poly(arylene ether nitrile), effectively reducing the dielectric constant of the system.

[0005] In summary, existing technologies all use porogens to create pores to lower the dielectric constant, but controlling the pores in porogens is complex. Excessively large pores can lead to insufficient material strength; while too small pores result in low cell density and porosity, insufficient to achieve low dielectric constants. Controlling the process is challenging, and thermodynamic performance needs to be improved. Summary of the Invention

[0006] In view of the above defects, the technical problem solved by the present invention is to provide a method for preparing a low-dielectric poly (arylene ether nitrile) composite material with good process controllability.

[0007] The method for preparing the low dielectric poly (arylene ether nitrile) composite material of the present invention comprises the following steps:

[0008] a. Preparation of C-FPEN@HGB filler: An ethanol dispersion of HGB is mixed with a C-FPEN resin solution, and the mixture is stirred and reacted at 40-60°C for 4-8 hours. The mixture is then solvent recovered, washed, and dried to obtain C-FPEN@HGB filler. The C-FPEN resin is a fluorinated poly(arylene ether nitrile) resin containing a carboxyl group, and the HGB is a hollow glass microsphere.

[0009] b. Preparation of a low-dielectric poly(arylene ether nitrile) composite material: C-FPEN@HGB filler, fluorinated poly(arylene ether nitrile) resin, and NMP solvent are mixed to obtain a composite solution; the composite solution is poured into water for precipitation, and the precipitate is washed and dried to obtain a low-dielectric poly(arylene ether nitrile) composite material.

[0010] In a specific embodiment, the structural formula of the C-FPEN resin is:

[0011]

[0012] Among them, m is 0.7 to 0.9, n is 0.1 to 0.3, and x is 20 to 200.

[0013] In a specific embodiment, the synthesis method of C-FPEN resin is: dihydric phenol and 2,6-dichlorobenzonitrile are added to NMP solvent for dissolution, potassium carbonate and toluene are added for dehydration at 170-180° C., the temperature is raised to 200-210° C. for polymerization reaction, and post-processing is performed to obtain C-FPEN resin, wherein the dihydric phenol is phenolphthalein and bisphenol AF.

[0014] In a specific embodiment, based on 100% by weight of the dihydric phenol, the weight percentage of phenolphthalein is 10-30%.

[0015] In a specific embodiment, in step a, the mass ratio of HGB to C-FPEN resin is 1.5 to 2.5:1; preferably, the mass ratio of HGB to C-FPEN resin is 2:1.

[0016] In a specific embodiment, in the C-FPEN solution of step a, the solvent is tetrahydrofuran, and the concentration is 0.02-0.05 g / mL; in the HGB ethanol dispersion, the concentration of HGB is 0.1-0.3 g / mL. Preferably, the concentration of HGB is 0.2 g / mL.

[0017] In a specific embodiment, in step a, the reaction is stirred at 50° C. for 6 h.

[0018] In a specific embodiment, in step b, the synthesis method of the fluorinated polyarylene ether nitrile resin is as follows: bisphenol AF and 2,6-dichlorobenzonitrile are added to NMP solvent for dissolution, potassium carbonate and toluene are added for dehydration at 170-180° C., the temperature is raised to 200-210° C. for polymerization reaction, and post-processing is performed to obtain the fluorinated polyarylene ether nitrile resin.

[0019] In a specific embodiment, in step b, based on 100% by weight of the low dielectric poly(arylene ether nitrile) composite material, the mass fraction of the C-FPEN@HGB filler is 10-40%.

[0020] The present invention also provides a low-dielectric polyarylethernitrile composite material prepared by the method of the present invention.

[0021] The low-dielectric polyarylethernitrile composite material of the present invention has a low dielectric constant and dielectric loss, good thermodynamic properties, good compatibility and dispersibility between the filler and the matrix resin, and can be used in the field of 5G communication technology, further expanding its use in the field of electronic materials.

[0022] Compared with the prior art, the present invention has the following beneficial effects:

[0023] 1. The method of the present invention can successfully obtain a core-shell structured C-FPEN@HGB filler, and a composite material with a significantly reduced dielectric constant (ε=1.93) and a relatively low dielectric loss (tanδ=0.0105) is prepared using the filler.

[0024] 2. The C-FPEN@HGB filler of the present invention is composed of C-FPEN resin and HGB bonded together by covalent bonds. The C-FPEN@HGB filler is perfectly encapsulated within the FPEN matrix resin, exhibiting excellent compatibility and dispersibility. While the C-FPEN@HGB filler has no significant effect on the glass transition temperature of the composite material, it can increase its thermal decomposition temperature to a certain extent (Td = 504-509°C).

[0025] 3. The composite material prepared by the surface organic modification of C-FPEN@HGB filler in the present invention has better mechanical properties and meets most application scenarios.

[0026] 4. The method of the present invention is simple and controllable, and can be applied to large-scale industrial production. BRIEF DESCRIPTION OF THE DRAWINGS

[0027] Figure 1 The SEM comparison pictures of the composite materials prepared in Example 1 and Comparative Example 4 of the present invention are shown. DETAILED DESCRIPTION

[0028] The method for preparing the low dielectric poly (arylene ether nitrile) composite material of the present invention comprises the following steps:

[0029] a. Preparation of C-FPEN@HGB filler: An ethanol dispersion of HGB is mixed with a C-FPEN resin solution, and the mixture is stirred and reacted at 40-60°C for 4-8 hours. The mixture is then solvent recovered, washed, and dried to obtain C-FPEN@HGB filler. The C-FPEN resin is a fluorinated poly(arylene ether nitrile) resin containing a carboxyl group, and the HGB is a hollow glass microsphere.

[0030] b. Preparation of a low-dielectric poly(arylene ether nitrile) composite material: C-FPEN@HGB filler, fluorinated poly(arylene ether nitrile) resin, and NMP solvent are mixed to obtain a composite solution; the composite solution is poured into water for precipitation, and the precipitate is washed and dried to obtain a low-dielectric poly(arylene ether nitrile) composite material.

[0031] The present invention introduces hollow glass microspheres and organically modifies their surfaces to create a functionalized filler with a core-shell structure. Using fluorinated poly(arylene ether nitrile) as the matrix material, a poly(arylene ether nitrile) composite material is prepared. This material not only exhibits a low dielectric constant and dielectric loss, but also exhibits good thermodynamic properties, and exhibits good compatibility and dispersibility between the filler and the matrix resin.

[0032] The present invention introduces a highly electronegative trifluoromethyl group into poly(arylene ether nitrile) to prepare a fluorinated poly(arylene ether nitrile) with a further reduced dielectric constant. The C-F bond in the trifluoromethyl group has a low dipole moment and low polarizability. Its strong electron-withdrawing effect and chemical inertness improve the material's polarity, solubility, hydrophobicity, and stability. Furthermore, the fluorinated poly(arylene ether nitrile) has excellent processing properties and can be formed by methods such as extrusion and injection molding.

[0033] In order to further reduce the dielectric constant of fluorinated poly(arylene ether nitrile), the present invention also prepares a low dielectric composite material by adding low dielectric nanoparticles into the polymer. Hollow glass microspheres (HGB) can be commercially available, which are hollow spherical particles with a true density of 0.20 to 0.60 g / cm 3 , the particle size is between 2 and 125 microns, and it has the advantages of low density, high temperature resistance, chemical corrosion resistance, and low electrical conductivity. Since air is the substance with the lowest known dielectric constant (ε=1), the hollow internal structure of HGB also makes it have the advantage of being a low dielectric filler. However, since hollow glass microspheres are inorganic silicate materials, when directly mixed with resin, the polarity of the two differs greatly, resulting in very weak interaction force at the interface, thereby reducing the performance of the composite material. Therefore, in order to obtain a low dielectric poly(arylene ether nitrile) composite material with good comprehensive performance, the present invention introduces hollow glass microspheres and organically modifies the surface thereof to prepare a poly(arylene ether nitrile) composite material with fluorinated poly(arylene ether nitrile) as the matrix material, thereby obtaining a composite material with low dielectric constant and dielectric loss, and the material has good thermodynamic properties, and the compatibility and dispersibility between the filler and the matrix resin are good.

[0034] In a specific embodiment, the structural formula of the C-FPEN resin is:

[0035]

[0036] Among them, m is 0.7 to 0.9, n is 0.1 to 0.3, and x is 20 to 200.

[0037] In one specific embodiment, the synthesis method of C-FPEN resin involves dissolving a dihydric phenol and 2,6-dichlorobenzonitrile in NMP solvent, then adding potassium carbonate and toluene for dehydration at 170-180°C, heating to 200-210°C for polymerization, and post-processing to obtain C-FPEN resin. The dihydric phenol is phenolphthalein and bisphenol AF. The poly(arylene ether nitrile) is introduced with carboxyl groups through phenolphthalein, significantly improving its compatibility with the surface of hollow glass microspheres.

[0038] In a specific embodiment, based on 100% by weight of the dihydric phenol, the weight percentage of phenolphthalein is 10-30%.

[0039] In a specific embodiment, in step a, the mass ratio of HGB to C-FPEN resin is 1.5 to 2.5: 1. Preferably, the mass ratio of HGB to C-FPEN resin is 2:1.

[0040] In a specific embodiment, in the C-FPEN solution of step a, the solvent is tetrahydrofuran, and the concentration is 0.02-0.05 g / mL; in the HGB ethanol dispersion, the concentration of HGB is 0.1-0.3 g / mL. Preferably, the concentration of HGB is 0.2 g / mL.

[0041] In a specific embodiment, in step a, the reaction is stirred at 50° C. for 6 h.

[0042] In a specific embodiment, in step b, the synthesis method of the fluorinated polyarylene ether nitrile resin is as follows: bisphenol AF and 2,6-dichlorobenzonitrile are added to NMP solvent for dissolution, potassium carbonate and toluene are added for dehydration at 170-180° C., the temperature is raised to 200-210° C. for polymerization reaction, and post-processing is performed to obtain the fluorinated polyarylene ether nitrile resin.

[0043] The post-treatment method described in the present invention is a conventional method in the art. In a specific embodiment of the present invention, the post-treatment is: pouring the reaction product after polymerization into water for precipitation, crushing and separating the resin by solid-liquid separation, and then washing and drying.

[0044] In a specific embodiment, in step b, based on 100% by weight of the low dielectric poly (arylene ether nitrile) composite material, the mass fraction of the C-FPEN@HGB filler is 10-40%.

[0045] The present invention also provides a low-dielectric polyarylethernitrile composite material prepared by the method of the present invention.

[0046] The low-dielectric polyarylethernitrile composite material of the present invention has a low dielectric constant and dielectric loss, good thermodynamic properties, good compatibility and dispersibility between the filler and the matrix resin, and can be used in the field of 5G communication technology, further expanding its use in the field of electronic materials.

[0047] The specific embodiments of the present invention are further described below in conjunction with examples, but the present invention is not limited to the scope of the examples.

[0048] Example 1

[0049] This embodiment provides a low-dielectric poly(arylene ether nitrile) composite material and its preparation method. First, the surface of hollow glass microspheres is chemically grafted with a carboxyl-containing fluorinated poly(arylene ether nitrile) to produce a C-FPEN@HGB filler coated with an organic layer. The core-shell C-FPEN@HGB filler is then added to a fluorinated poly(arylene ether nitrile) matrix. Finally, a low-dielectric poly(arylene ether nitrile) composite material with a significantly reduced dielectric constant is obtained.

[0050] The specific steps include:

[0051] Step 1: Synthesis of carboxyl-containing fluorinated poly (arylene ether nitrile): 20% phenolphthalein, 80% bisphenol AF, and 2,6-dichlorobenzonitrile were dissolved in NMP solvent, followed by addition of potassium carbonate and toluene for dehydration at 180°C, followed by polymerization at 205°C, and post-treatment to obtain C-FPEN resin.

[0052] Step 2: Preparation of C-FPEN@HGB filler: HGB (concentration: 0.2 g / mL) uniformly dispersed in ethanol was added to a C-FPEN solution in tetrahydrofuran (concentration: 0.02 g / mL). The mixture was stirred continuously at 50°C for 6 h. Finally, the C-FPEN@HGB filler was obtained by solvent recovery, washing, and drying. The mass ratio of HGB to C-FPEN resin was 2:1.

[0053] Step 3: Synthesis of fluorinated polyarylethernitrile: bisphenol AF and 2,6-dichlorobenzonitrile were dissolved in NMP solvent, potassium carbonate and toluene were added to dehydrate at 180°C, and the temperature was raised to 205°C for polymerization reaction. After post-treatment, FPEN resin was obtained.

[0054] Step 4: Add 40% C-FPEN@HGB filler by mass to NMP solvent and stir for 2 hours to obtain a suspension; then add FPEN resin and stir continuously for 3 hours to obtain a composite solution; finally, pour the composite solution into water for precipitation, and obtain a white granular product after post-treatment.

[0055] Example 2

[0056] This embodiment provides a low-dielectric poly(arylene ether nitrile) composite material and a preparation method thereof. First, the surface of hollow glass microspheres is chemically grafted with a carboxyl-containing fluorinated poly(arylene ether nitrile) to obtain a C-FPEN@HGB filler coated with an organic layer. Then, the C-FPEN@HGB filler having a core-shell structure is added to a fluorinated poly(arylene ether nitrile) matrix. Finally, a low-dielectric poly(arylene ether nitrile) composite material having a significantly reduced dielectric constant is obtained.

[0057] The specific steps include:

[0058] Step 1: Synthesis of carboxyl-containing fluorinated poly (arylene ether nitrile): 30% phenolphthalein, 70% bisphenol AF, and 2,6-dichlorobenzonitrile were dissolved in NMP solvent, followed by addition of potassium carbonate and toluene for dehydration at 180°C, followed by polymerization at 205°C, and post-treatment to obtain C-FPEN resin.

[0059] Step 2: Preparation of C-FPEN@HGB filler: HGB (concentration: 0.2 g / mL) uniformly dispersed in ethanol was added to a C-FPEN solution in tetrahydrofuran (concentration: 0.03 g / mL). The mixture was stirred continuously at 50°C for 6 h. Finally, the C-FPEN@HGB filler was obtained through solvent recovery, washing, and drying. The mass ratio of HGB to C-FPEN resin was 2:1.

[0060] Step 3: Synthesis of fluorinated polyarylethernitrile: bisphenol AF and 2,6-dichlorobenzonitrile were dissolved in NMP solvent, potassium carbonate and toluene were added to dehydrate at 180°C, and the temperature was raised to 205°C for polymerization reaction. After post-treatment, FPEN resin was obtained.

[0061] Step 4: Add 30% C-FPEN@HGB filler by mass to NMP solvent and stir for 2 hours to obtain a suspension; then add FPEN resin and stir continuously for 3 hours to obtain a composite solution; finally, pour the composite solution into water for precipitation, and obtain a white granular product after post-treatment.

[0062] Example 3

[0063] This embodiment provides a low-dielectric poly(arylene ether nitrile) composite material and a preparation method thereof. First, the surface of hollow glass microspheres is chemically grafted with a carboxyl-containing fluorinated poly(arylene ether nitrile) to obtain a C-FPEN@HGB filler coated with an organic layer. Then, the C-FPEN@HGB filler having a core-shell structure is added to a fluorinated poly(arylene ether nitrile) matrix. Finally, a low-dielectric poly(arylene ether nitrile) composite material having a significantly reduced dielectric constant is obtained.

[0064] The specific steps include:

[0065] Step 1: Synthesis of carboxyl-containing fluorinated poly (arylene ether nitrile): 20% phenolphthalein, 80% bisphenol AF, and 2,6-dichlorobenzonitrile were dissolved in NMP solvent, followed by addition of potassium carbonate and toluene for dehydration at 180°C, followed by polymerization at 205°C, and post-treatment to obtain C-FPEN resin.

[0066] Step 2: Preparation of C-FPEN@HGB filler: HGB (concentration: 0.2 g / mL) uniformly dispersed in ethanol was added to a C-FPEN solution in tetrahydrofuran (concentration: 0.02 g / mL). The mixture was stirred continuously at 50°C for 6 h. Finally, the C-FPEN@HGB filler was obtained by solvent recovery, washing, and drying. The mass ratio of HGB to C-FPEN resin was 2:1.

[0067] Step 3: Synthesis of fluorinated polyarylethernitrile: bisphenol AF and 2,6-dichlorobenzonitrile were dissolved in NMP solvent, potassium carbonate and toluene were added to dehydrate at 180°C, and the temperature was raised to 205°C for polymerization reaction. After post-treatment, FPEN resin was obtained.

[0068] Step 4: Add 10% by mass of C-FPEN@HGB filler to NMP solvent and stir for 2 hours to obtain a suspension; then add FPEN resin and stir continuously for 3 hours to obtain a composite solution; finally, pour the composite solution into water for precipitation, and obtain a white granular product after post-treatment.

[0069] Comparative Example 1

[0070] This comparative example provides a low-dielectric poly(arylene ether nitrile) composite material and a preparation method thereof. First, hollow glass microspheres are surface-treated with a dilute solution of fluorinated poly(arylene ether nitrile) to obtain a FPEN@HGB filler coated with an organic layer on the surface; then, the FPEN@HGB filler is added to a fluorinated poly(arylene ether nitrile) matrix; and finally, the low-dielectric poly(arylene ether nitrile) composite material is obtained through post-treatment.

[0071] The specific steps include:

[0072] Step 1: Synthesis of fluorinated polyarylether nitrile (FPEN resin): bisphenol AF and 2,6-dichlorobenzonitrile were dissolved in NMP solvent, potassium carbonate and toluene were added for dehydration at 180°C, and the temperature was raised to 205°C for polymerization reaction. After post-treatment, FPEN resin was obtained.

[0073] Step 2: Preparation of FPEN@HGB filler: HGB (concentration of 0.2 g / mL) uniformly dispersed in ethanol was added to a tetrahydrofuran solution of FPEN (concentration of 0.02 g / mL). The mixture was stirred continuously at 50°C for 6 h. Finally, the FPEN@HGB filler was obtained by solvent recovery, washing, and drying. The mass ratio of HGB to FPEN resin was 2:1.

[0074] Step 3: Add 40% by mass of FPEN@HGB filler to NMP solvent and stir for 2 hours to obtain a suspension; then add FPEN resin and stir continuously for 3 hours to obtain a composite solution; finally, pour the composite solution into water for precipitation, and obtain a white granular product after post-treatment.

[0075] Comparative Example 2

[0076] In this comparative example, a low-dielectric poly(arylene ether nitrile) material was prepared according to the method described in patent CN110105575A. First, a fluorinated poly(arylene ether nitrile sulfone) block copolymer was synthesized; then, the fluorinated poly(arylene ether nitrile sulfone) block copolymer was blended and dispersed with a porogen in a solution; the mixed solution was then prepared into a porous membrane; and finally, a low-dielectric poly(arylene ether nitrile) thin film material was obtained through post-processing.

[0077] The specific steps include:

[0078] Step 1: Synthesis of a fluorinated poly(aryl ether nitrile sulfone) block copolymer: Dissolve 2,6-dichlorobenzonitrile, 4,4-dichlorodiphenyl sulfone, and bisphenol AF in NMP. Dehydrate with potassium carbonate and toluene at 180°C. Heat to 205°C for polymerization. Post-treatment yields a fluorinated poly(aryl ether nitrile sulfone) block copolymer. The molar ratio of 2,6-dichlorobenzonitrile, 4,4-dichlorodiphenyl sulfone, and bisphenol AF is 1:9:10.

[0079] Step 2: Add the fluorinated poly(arylene ether nitrile sulfone) block copolymer to N,N-dimethylformamide to obtain a 10 wt% solution, then add 2% porogen polyvinyl alcohol to the system and mechanically stir at 300 r / min for 2 h until completely dissolved.

[0080] Step 3: Pour the mixed solution obtained in step 2 onto a glass plate, scrape out a liquid film of about 300 μm using a wet film preparation device and soak it in an ethanol-water solution (ethanol: water = 1:6). After the liquid film becomes a solid film, peel off the glass plate and soak it in deionized water for 2 days to obtain a polyarylethernitrile porous membrane.

[0081] Step 4: Remove the poly(arylene ether nitrile) porous membrane and drain the water, then place it in an oven at 100°C for 12 hours to obtain a low-dielectric poly(arylene ether nitrile) film material. This material has poor mechanical properties and cannot be subjected to mechanical testing.

[0082] The low dielectric poly(arylene ether nitrile) composite materials of Example 1 and Comparative Example 1 were pressed to prepare samples, and the mechanical properties, thermal properties, and dielectric properties of the samples were tested at room temperature. The performance comparison results of the low dielectric poly(arylene ether nitrile) composite materials are shown in Table 1 below:

[0083] Table 1 Comparison of properties of low dielectric poly(arylene ether nitrile) composite materials

[0084] Test items Test Method Example 1 Example 2 Example 3 Comparative Example 1 Comparative Example 2 Tensile strength (MPa) GB / T1040.2 46 53 69 38 -- Elongation at break (%) GB / T1040.2 5.4 7.3 8.8 3.9 -- Glass transition temperature (℃) GB / T19466 178 177 179 178 197 Thermal decomposition temperature (℃) TGA 509 508 504 508 517 Dielectric constant (1kHz) IEC 62631-2-1 1.93 2.07 2.35 1.96 1.47 Dielectric loss (1kHz) IEC 62631-2-1 0.0105 0.0104 0.0081 0.0147 0.0041

[0085] From the test results in the above table, we can see that the preparation method used in the embodiment, which introduces hollow glass microspheres, has no significant effect on the glass transition temperature of the composite material, but increases its thermal decomposition temperature (Td = 504-509°C) to a certain extent. With the increase of filler, the dielectric constant of the composite material is significantly reduced (ε = 1.93), and a low dielectric loss (tanδ = 0.0105) is maintained. Compared with Comparative Example 1, the composite material prepared from hollow glass microspheres after surface organic modification has better mechanical properties. Comparative Example 2 uses a porogen to form pores in the polyarylether nitrile material. Although it reduces the dielectric constant, it loses the mechanical properties of the material, limiting its application. This shows that the present invention successfully obtains a low-dielectric polyarylether nitrile composite material with good comprehensive performance.

Claims

1. A method for preparing a low dielectric poly(arylene ether nitrile) composite material, characterized in that: The following steps are involved: a. Preparation of C-FPEN@HGB filler: An ethanol dispersion of HGB is mixed with a C-FPEN resin solution, and the mixture is stirred at 40-60°C for 4-8 hours. The mixture is then solvent recovered, washed, and dried to obtain C-FPEN@HGB filler. The C-FPEN resin is a fluorinated poly(arylene ether nitrile) resin containing a carboxyl group, and the HGB is a hollow glass microsphere. b. Preparation of a low-dielectric poly(arylene ether nitrile) composite material: C-FPEN@HGB filler, fluorinated poly(arylene ether nitrile) resin, and NMP solvent are mixed to obtain a composite solution; the composite solution is poured into water for precipitation, and the precipitate is washed and dried to obtain a low-dielectric poly(arylene ether nitrile) composite material.

2. The method for preparing the low dielectric poly(arylene ether nitrile) composite material according to claim 1, wherein: The structural formula of the C-FPEN resin is: Among them, m is 0.7 to 0.9, n is 0.1 to 0.3, and x is 20 to 200.

3. The method for preparing the low dielectric poly(arylene ether nitrile) composite material according to claim 1, wherein: The synthesis method of C-FPEN resin is as follows: dihydric phenol and 2,6-dichlorobenzonitrile are added to NMP solvent for dissolution, potassium carbonate and toluene are added for dehydration at 170-180°C, the temperature is raised to 200-210°C for polymerization reaction, and post-processing is performed to obtain C-FPEN resin, wherein the dihydric phenol is phenolphthalein and bisphenol AF.

4. The method for preparing the low dielectric poly(arylene ether nitrile) composite material according to claim 3, wherein: Based on 100% by weight of the dihydric phenol, the weight percentage of phenolphthalein is 10-30%.

5. The method for preparing the low dielectric poly(arylene ether nitrile) composite material according to claim 1, wherein: In step a, the mass ratio of HGB to C-FPEN resin is 1.5-2.5:

1.

6. The method for preparing the low dielectric poly(arylene ether nitrile) composite material according to claim 5, wherein: The mass ratio of HGB to C-FPEN resin is 2:

1.

7. The method for preparing a low dielectric poly(arylene ether nitrile) composite material according to claim 1, wherein: In the C-FPEN resin solution of step a, the solvent is tetrahydrofuran, and the concentration is 0.02-0.05 g / mL; In the HGB ethanol dispersion of step a, the concentration of HGB is 0.1-0.3 g / mL.

8. The method for preparing the low dielectric poly(arylene ether nitrile) composite material according to claim 7, wherein: The concentration of HGB was 0.2 g / mL.

9. The method for preparing a low dielectric poly(arylene ether nitrile) composite material according to claim 1, wherein: In step a, the reaction was stirred at 50°C for 6 h.

10. The method for preparing a low dielectric poly(arylene ether nitrile) composite material according to claim 1, wherein: In step b, the synthesis method of the fluorinated polyarylether nitrile resin is as follows: bisphenol AF and 2,6-dichlorobenzonitrile are added to NMP solvent for dissolution, potassium carbonate and toluene are added for dehydration at 170-180° C., the temperature is raised to 200-210° C. for polymerization reaction, and post-processing is performed to obtain the fluorinated polyarylether nitrile resin.

11. The method for preparing the low dielectric poly(arylene ether nitrile) composite material according to claim 1, wherein: In step b, based on the weight of the low dielectric poly(arylene ether nitrile) composite material being 100%, the mass fraction of the C-FPEN@HGB filler is 10-40%. 12 . The low dielectric poly(arylene ether nitrile) composite material prepared by the method for preparing the low dielectric poly(arylene ether nitrile) composite material according to claim 1 .

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