A crosslinked fluorine-containing polyarylene ether film material and a preparation method and application thereof

Abstract

The application provides a crosslinked fluorine-containing polyarylene ether film material, a molecular formula of the crosslinked fluorine-containing polyarylene ether film material is shown in formula 1: in the structural formula 1, the content x is 0.1-0.4, 1-x is 0.6-0.9, and n is 40-70. The crosslinked fluorine-containing polyarylene ether film material has low dielectric constant, low dielectric loss and low water absorption, and has excellent thermodynamic performance, and has potential application value in the fields of communication and microelectronics.

Description

Technical Field

[0001] This invention belongs to the field of polyarylene ether membrane materials and their preparation, and particularly relates to a cross-linked fluorinated polyarylene ether membrane material, its preparation method, and its application. Background Technology

[0002] With the advent of the fifth-generation communication technology era and the rapid development of very large-scale integrated circuits, the size of electronic devices in circuits is gradually becoming smaller, even miniaturized. However, the miniaturization of circuits leads to increased delay and power consumption in resistors and capacitors. Therefore, there is an urgent need to develop high-performance, low-dielectric-constant materials to reduce these adverse effects and improve the performance of electronic devices. Traditional polyarylether resins contain a large number of aromatic rings, resulting in highly rigid molecular chains. Therefore, they possess excellent dimensional stability, abrasion resistance, thermal stability, and superior mechanical properties. The aryl ether bonds in the structure can, to some extent, ensure the flexibility of the molecular chains. Moreover, polyarylethers exhibit low dielectric constants and dielectric losses over a wide frequency range, making them suitable for applications in low-dielectric materials.

[0003] However, with the development of communication and microelectronics technologies, the dielectric constant of traditional polyarylene ethers is around 3 to 5, which can no longer meet the requirements. Therefore, in order to further develop polyarylene ether interlayer dielectric materials, it is necessary to optimize the molecular structure to improve its dielectric properties. Summary of the Invention

[0004] The purpose of this invention is to address the above-mentioned shortcomings by providing a cross-linked fluorinated polyarylene ether membrane material, its preparation method, and its applications. By introducing low-polarity trifluoroisopropyl and perfluorobiphenyl structures with large free volume into the polymer structure, this type of polymer exhibits low surface free energy, dielectric constant, and strong dimensional and thermal stability. Simultaneously, cross-linkable allyl side groups are introduced into the polymer structure. The allyl groups serve as cross-linking sites, undergoing cross-linking reactions to form a cross-linked network, restricting chain segment movement, further reducing the dielectric constant, and improving dielectric properties. This type of polyarylene ether polymer has significant potential application value in the fields of communication and microelectronics.

[0005] This invention provides a cross-linked fluorinated polyarylene ether membrane material, the molecular formula of which is shown in Formula 1:

[0006]

[0007] In the structural formula 1, the content of x = 0.1 to 0.4, 1-x = 0.6 to 0.9, and n = 40 to 70.

[0008] The above-mentioned crosslinked fluorinated polyarylene ether membrane material is prepared by high-temperature crosslinking of fluorinated polyarylene ether containing an allyl structure. The molecular structural formula of the fluorinated polyarylene ether containing an allyl structure is shown in Formula 2:

[0009]

[0010] The structural formula 2 is divided into crosslinkable structural units and non-crosslinkable structural units. The content of the crosslinkable structural units is x = 0.1 to 0.4, and the content of the non-crosslinkable structural units is 1-x = 0.6 to 0.9, n = 40 to 70.

[0011] The second aspect of this invention provides a method for preparing cross-linked fluorinated polyarylether membrane materials, the synthetic route of which is as follows:

[0012]

[0013] The specific steps are as follows:

[0014] Step (1) Preparation of crosslinkable fluorinated polyarylene ethers with allyl structure: Perfluorobiphenyl, bisphenol AF, 2,2'-diallylbisphenol A, potassium carbonate, and N-methyl-2-pyrrolidone were added to a three-necked flask equipped with a mechanical stirrer, a water condenser, and a nitrogen inlet and outlet and stirred to react. After the reaction was completed, a viscous polymer solution was obtained. The polymer solution was slowly poured into ethanol to settle. After filtration, washing, and drying, fibrous crosslinkable fluorinated polyarylene ethers with allyl structure were obtained.

[0015] Step (2) Preparation of crosslinkable fluorinated polyaryl ether film with allyl structure: The polyaryl ether obtained in step (1) is heated and fully dissolved in N-methyl-2-pyrrolidone, then filtered with a sintered funnel to obtain a uniform solution. The solution is cast onto a glass substrate, then placed in an oven to dry. After natural cooling, the film is peeled off from the glass substrate to obtain crosslinkable fluorinated polyaryl ether film with allyl structure.

[0016] Step (3) Preparation of cross-linked fluorinated polyarylene ether membrane material: The allyl-containing cross-linkable fluorinated polyarylene ether film obtained in step (2) is vacuum dried at high temperature and cross-linked to obtain cross-linked fluorinated polyarylene ether membrane material.

[0017] Furthermore, the molar amount of the perfluorobiphenyl is equal to the sum of the molar amounts of 2,2'-diallylbisphenol A and bisphenol AF, and the molar ratio of 2,2'-diallylbisphenol A to bisphenol AF is 1:9 to 4:6.

[0018] Furthermore, the molar amount of potassium carbonate is 1 to 2 times the molar amount of perfluorobiphenyl.

[0019] Furthermore, the amount of N-methyl-2-pyrrolidone used is 3 to 5 times the total mass of perfluorobiphenyl, bisphenol AF and 2,2'-diallylbisphenol A.

[0020] Furthermore, the reaction conditions are: reaction temperature 100-120℃, reaction time 4-6 hours.

[0021] Furthermore, the drying conditions in the oven are as follows: drying at 80℃, 100℃, 120℃, 140℃, 160℃, 180℃, and 200℃ for 2 hours respectively.

[0022] Furthermore, in step (2), the amount of N-methyl-2-pyrrolidone used is 10-15 times the amount of crosslinkable fluorinated polyarylene ether containing an allyl structure.

[0023] Furthermore, in step (3), the crosslinking conditions are: under vacuum, at a temperature of 250–260°C.

[0024] A third aspect of the present invention also provides an application of a cross-linked fluorinated polyarylene ether membrane material, which can be used as a membrane material in the fields of communication and microelectronics.

[0025] Beneficial effects of this invention:

[0026] (1) The allyl-containing crosslinkable fluorinated polyarylene ether provided by the present invention reduces the polarity and surface free energy of the polymer material by introducing trifluoroisopropyl and perfluorobiphenyl structures, thereby reducing the dielectric constant and dielectric loss of the polymer material and improving the hydrophobic properties.

[0027] (2) The allyl-containing crosslinkable fluorinated polyaryl ether provided by the present invention, by introducing a crosslinkable allyl structure, with allyl as a crosslinking site, undergoes a crosslinking reaction to form a crosslinking network, restricting chain segment movement, and further reducing dielectric constant, dielectric loss and water absorption rate.

[0028] (3) The polyarylether polymer prepared by this invention uses readily available starting materials and relatively simple synthetic routes. The product is easy to purify and separate, has a high yield, is stable at room temperature, and is easy to industrialize. Attached Figure Description

[0029] Figure 1 It is the allyl-containing crosslinkable fluorinated polyarylene ether (PAE10) in Example 1. 1 H NMR spectrum;

[0030] Figure 2 It is the allyl-containing crosslinkable fluorinated polyarylene ether (PAE20) in Example 2. 1 H NMR spectrum;

[0031] Figure 3 It is the allyl-containing crosslinkable fluorinated polyarylene ether (PAE30) in Example 3. 1 H NMR spectrum;

[0032] Figure 4 It is the allyl-containing crosslinkable fluorinated polyarylene ether (PAE40) in Example 4. 1 H NMR spectrum;

[0033] Figure 5 These are the infrared spectra of the allyl-containing crosslinkable fluorinated polyarylene ethers (UCL-PAE10-40) in Examples 1-4;

[0034] Figure 6 The infrared spectra of the crosslinkable fluorinated polyarylene ether containing allyl structure (UCL-PAE40) and the crosslinked fluorinated polyarylene ether membrane material (CL-PAE40) in Example 4 are compared.

[0035] Figure 7 The graph shows the relationship between the dielectric constant and the electric field frequency of the crosslinkable fluorinated polyarylene ether film (UCL-PAE10-40) and the crosslinked fluorinated polyarylene ether film material (CL-PAE10-40) with allyl structure in Examples 1-4.

[0036] Figure 8 This is the C1s XPS spectrum of the allyl-containing crosslinkable fluorinated polyarylene ether membrane (UCL-PAE40) in Example 4;

[0037] Figure 9 This is the C1s XPS spectrum of the cross-linked fluorinated polyarylether membrane material (CL-PAE40) in Example 4. Detailed Implementation

[0038] To make the above-mentioned objectives, features and advantages of the present invention more apparent and understandable, the specific embodiments of the present invention will be described in detail below with reference to the examples in the specification. Unless otherwise specified, the methods described are conventional methods, and the raw materials described are available from publicly available commercial sources unless otherwise specified.

[0039] The term "an embodiment" or "embodiment" as used herein refers to a specific feature, structure, or characteristic that may be included in at least one implementation of the invention. The phrase "in one embodiment" appearing in different places throughout this specification does not necessarily refer to the same embodiment, nor is it a single or selective embodiment that is mutually exclusive with other embodiments.

[0040] The sources of the pharmaceuticals and reagents described in the examples are as follows:

[0041] 2,2-Bis(4-hydroxyphenyl)hexafluoropropane (bisphenol AF): Tokyo Chemical Industry Co., Ltd., purity >98%.

[0042] 2,2'-Dielylbisphenol A: Shanghai Maclean Biochemical Technology Co., Ltd., purity 90%.

[0043] Perfluorinated biphenyls: Wuhan Changcheng Chemical Technology Development Co., Ltd., purity > 98%.

[0044] N-Methyl-2-pyrrolidone (NMP): Shanghai Lingfeng Chemical Reagent Co., Ltd., purity ≥99%.

[0045] Anhydrous potassium carbonate (K2CO3): Shanghai Lingfeng Chemical Reagent Co., Ltd., purity ≥99%.

[0046] The specific preparation method is as follows:

[0047] Step (1) Preparation of crosslinkable fluorinated polyarylene ethers with allyl structure: Perfluorobiphenyl, bisphenol AF, 2,2'-diallylbisphenol A, potassium carbonate, and N-methyl-2-pyrrolidone were added to a three-necked flask equipped with a mechanical stirrer, a water condenser, and a nitrogen inlet and outlet and stirred to react. After the reaction was completed, a viscous polymer solution was obtained. The polymer solution was slowly poured into ethanol to settle. After filtration, washing, and drying, fibrous crosslinkable fluorinated polyarylene ethers with allyl structure were obtained.

[0048] Step (2) Preparation of crosslinkable fluorinated polyaryl ether film with allyl structure: The polyaryl ether obtained in step (1) is heated and fully dissolved in N-methyl-2-pyrrolidone. Then, a uniform solution is obtained by filtering with a sintered glass funnel. The solution is cast onto a glass substrate and then placed in an oven to dry. After natural cooling, the film is peeled off from the glass substrate to obtain crosslinkable fluorinated polyaryl ether film with allyl structure.

[0049] Step (3) Preparation of cross-linked fluorinated polyarylene ether membrane material: The allyl-containing cross-linkable fluorinated polyarylene ether film obtained in step (2) is vacuum dried at high temperature and cross-linked to obtain cross-linked fluorinated polyarylene ether membrane material.

[0050] Preferably, the molar amount of the perfluorobiphenyl is equal to the sum of the molar amounts of 2,2'-diallylbisphenol A and bisphenol AF, and the molar ratio of 2,2'-diallylbisphenol A to bisphenol AF is 1:9 to 4:6; the molar amount of potassium carbonate is 1 to 2 times the molar amount of perfluorobiphenyl; the amount of N-methyl-2-pyrrolidone is 3 to 5 times the total mass of perfluorobiphenyl, bisphenol AF, and 2,2'-diallylbisphenol A; and the reaction conditions are: The temperature should be 100-120℃, and the reaction time should be 4-6 hours. The drying conditions of the oven are: drying at 80℃, 100℃, 120℃, 140℃, 160℃, 180℃, and 200℃ for 2 hours respectively. In step (2), the amount of N-methyl-2-pyrrolidone is 10-15 times the amount of crosslinkable fluorinated polyarylene ether containing allyl structure. In step (3), the crosslinking conditions are: under vacuum, at a temperature of 250-260℃.

[0051] The following examples illustrate the specific amounts of raw materials and reaction conditions.

[0052] Example 1

[0053] Step (1) Preparation of crosslinkable fluorinated polyarylene ether (PAE10) containing allyl structure

[0054] Perfluorobiphenyl (4.0093 g, 12 mmol), bisphenol AF (3.6313 g, 10.8 mmol), 2,2'-diallylbisphenol A (0.3701 g, 1.2 mmol), potassium carbonate (2.6536 g, 19.2 mmol), and 26 mL of N-methyl-2-pyrrolidone were added to a 100 mL three-necked flask equipped with a mechanical stirrer, a water condenser, and nitrogen inlet / outlet. The reaction was stirred at 100 °C for 4 hours. After the reaction was completed, the polymer solution was poured into ethanol to precipitate, and then further filtered, washed, and dried to obtain a fibrous, allyl-containing, crosslinkable fluorinated polyarylene ether (PAE10). Molar yield: 87%; 1H-NMR (CDCl3, 400 MHz) is shown in the attached figure. Figure 1 As shown, the data were recorded using a Bruker AVANCE III 400M digital nuclear magnetic resonance spectrometer with CDCl3 as the solvent. 1 H NMR spectrum; FT-IR such as Figure 5 As shown.

[0055] Step (2) Preparation of the allyl-containing crosslinkable fluorinated polyarylene ether film (UCL-PAE10): The obtained dry polymer (2g) was heated and fully dissolved in N-methyl-2-pyrrolidone (20mL), and then filtered through a sintered glass funnel to obtain a homogeneous solution. The homogeneous solution was cast onto a glass substrate (approximately 8cm × 8cm inner diameter), and then placed in a flat-bottomed oven and dried at 80℃, 100℃, 120℃, 140℃, 160℃, 180℃, and 200℃ for 2 hours respectively. After natural cooling, the film (approximately 0.25mm thick) was peeled off from the glass substrate to obtain the allyl-containing crosslinkable fluorinated polyarylene ether film (UCL-PAE10). The prepared 0.25mm (UCL-PAE10) film was used for thermal and dielectric property testing, and the prepared 0.2mm (UCL-PAE10) film was used for infrared characterization. The preparation method was the same as described above.

[0056] Step (3) Preparation of cross-linked fluorinated polyarylether membrane material (CL-PAE10)

[0057] The above-mentioned film was vacuum dried at 260°C for 2 hours and then subjected to a crosslinking reaction to prepare a crosslinked fluorinated polyarylether membrane material (CL-PAE10).

[0058] Example 2

[0059] Step (1) Preparation of crosslinkable fluorinated polyarylene ether (PAE20) containing allyl structure

[0060] Perfluorobiphenyl (4.0093 g, 12 mmol), bisphenol AF (3.2278 g, 9.6 mmol), 2,2'-diallylbisphenol A (0.7402 g, 2.4 mmol), potassium carbonate (2.6536 g, 19.2 mmol), and 26 mL of N-methyl-2-pyrrolidone were added to a 100 mL three-necked flask equipped with a mechanical stirrer, a water condenser, and nitrogen inlet / outlet. The reaction was stirred at 110 °C for 4 hours. After the reaction was completed, the polymer solution was poured into ethanol to precipitate, and then further filtered, washed, and dried to obtain a fibrous, allyl-containing, crosslinkable fluorinated polyarylene ether (PAE20). Molar yield: 88%. 1 H-NMR (CDCl3, 400MHz) as attached Figure 2 As shown; FT-IR as Figure 5 As shown.

[0061] Step (2) Preparation of the allyl-containing crosslinkable fluorinated polyarylene ether film (UCL-PAE20): The obtained dry polymer (2g) was heated and fully dissolved in N-methyl-2-pyrrolidone (20mL), and then filtered through a sintered glass funnel to obtain a homogeneous solution. The homogeneous solution was cast onto a glass substrate (approximately 8cm × 8cm in inner diameter), and then placed in a flat-bottomed oven and dried at 80℃, 100℃, 120℃, 140℃, 160℃, 180℃, and 200℃ for 2 hours respectively. After natural cooling, the film (approximately 0.25mm thick) was peeled off from the glass substrate to obtain the allyl-containing crosslinkable fluorinated polyarylene ether film (UCL-PAE20). The prepared 0.25mm (UCL-PAE20) film was used for thermal and dielectric property testing, and the prepared 0.2mm (UCL-PAE20) film was used for infrared characterization. The preparation method was the same as described above.

[0062] Step (3) Preparation of cross-linked polymer film (CL-PAE20)

[0063] The above-mentioned film was vacuum dried at 260°C for 2 hours and then further heat-treated to prepare a cross-linked fluorinated polyarylether film material (CL-PAE20).

[0064] Example 3

[0065] Step (1) Preparation of crosslinkable fluorinated polyarylene ether (PAE30) containing allyl structure

[0066] Perfluorobiphenyl (4.0093 g, 12 mmol), bisphenol AF (2.8243 g, 8.4 mmol), 2,2'-diallylbisphenol A (1.1103 g, 3.6 mmol), potassium carbonate (2.6536 g, 19.2 mmol), and 26 mL of N-methyl-2-pyrrolidone were added to a 100 mL three-necked flask equipped with a mechanical stirrer, a water condenser, and nitrogen inlet / outlet. The reaction was stirred at 110 °C for 5 hours. After the reaction was completed, the polymer solution was poured into ethanol to precipitate, and then further filtered, washed, and dried to obtain a fibrous, allyl-containing, crosslinkable fluorinated polyarylene ether (PAE30). Molar yield: 87%. 1 H-NMR (CDCl3, 400MHz) as attached Figure 3 As shown; FT-IR as Figure 5 As shown.

[0067] Step (2) Preparation of the allyl-containing crosslinkable fluorinated polyarylene ether film (UCL-PAE30): The obtained dry polymer (2g) was heated and fully dissolved in N-methyl-2-pyrrolidone (20mL), and then filtered through a sintered glass funnel to obtain a homogeneous solution. The homogeneous solution was cast onto a glass substrate (approximately 8cm × 8cm in inner diameter), and then placed in a flat-bottomed oven and dried at 80℃, 100℃, 120℃, 140℃, 160℃, 180℃, and 200℃ for 2 hours respectively. After natural cooling, the film (approximately 0.25mm thick) was peeled off from the glass substrate to obtain the allyl-containing crosslinkable fluorinated polyarylene ether film (UCL-PAE30). The prepared 0.25mm (UCL-PAE30) film was used for thermal and dielectric property testing, and the prepared 0.2mm (UCL-PAE30) film was used for infrared characterization. The preparation method was the same as described above.

[0068] Step (3) Preparation of cross-linked fluorinated polyarylether membrane material (CL-PAE30)

[0069] The above-mentioned film was vacuum dried at 260°C for 2 hours and then further heat-treated to prepare a cross-linked fluorinated polyarylether film material (CL-PAE30).

[0070] Example 4

[0071] Step (1) Preparation of crosslinkable fluorinated polyarylene ether (PAE40) containing allyl structure

[0072] Perfluorobiphenyl (4.0093 g, 12 mmol), bisphenol AF (2.4208 g, 7.2 mmol), 2,2'-diallylbisphenol A (1.4804 g, 4.8 mmol), potassium carbonate (2.6536 g, 19.2 mmol), and 26 mL of N-methyl-2-pyrrolidone were added to a 100 mL three-necked flask equipped with a mechanical stirrer, a water condenser, and nitrogen inlet / outlet. The reaction was stirred at 120 °C for 6 hours. After the reaction was completed, the polymer solution was poured into ethanol to precipitate, and then further filtered, washed, and dried to obtain a fibrous, allyl-containing, crosslinkable fluorinated polyarylene ether (PAE40). Molar yield: 86%. 1 H-NMR (CDCl3, 400MHz) as attached Figure 4 As shown; FT-IR as Figure 5 As shown.

[0073] Step (2) Preparation of the allyl-containing crosslinkable fluorinated polyarylene ether film (UCL-PAE40): The obtained dry polymer (2g) was heated and fully dissolved in N-methyl-2-pyrrolidone (20mL), and then filtered through a sintered glass funnel to obtain a homogeneous solution. The homogeneous solution was cast onto a glass substrate (approximately 8cm × 8cm in inner diameter), and then placed in a flat-bottomed oven and dried at 80℃, 100℃, 120℃, 140℃, 160℃, 180℃, and 200℃ for 2 hours respectively. After natural cooling, the film (approximately 0.25mm thick) was peeled off from the glass substrate to obtain the allyl-containing crosslinkable fluorinated polyarylene ether film (UCL-PAE40). The prepared 0.25mm (UCL-PAE40) film was used for thermal and dielectric property testing, and the prepared 0.2mm (UCL-PAE40) film was used for infrared characterization. The preparation method was the same as described above.

[0074] Step (3) Preparation of cross-linked fluorinated polyarylether membrane material (CL-PAE40)

[0075] The above-mentioned film was vacuum dried at 260°C for 2 hours and then further heat-treated to prepare a cross-linked fluorinated polyarylether film material (CL-PAE40).

[0076] NMR analysis: Figure 1-4 In the range of 6.5–8.0 ppm, the chemical shifts are attributed to protons on the aromatic ring. The chemical shifts at 6.01 ppm, 5.07 ppm, and 3.53 ppm are characteristic peaks for allyl groups. The chemical shift at 1.65 ppm is a characteristic peak for methyl groups.

[0077] Figure 5 The infrared spectra of the allyl-containing crosslinkable fluorinated polyarylene ether membranes (UCL-PAE10-40) in Examples 1-4 are shown.

[0078] Analysis: At 1695cm -1 Typical vibrational absorption peaks of the C=C bond appeared at 1607, 1649, 1506, and 1480 cm⁻¹. -1 An absorption peak for the skeletal vibration of the benzene ring appeared at 1223 cm⁻¹. -1 and 1070cm -1 Asymmetric and symmetric vibrational peaks of the aryl ether bond were observed. (1172 cm⁻¹) -1 The characteristic peak at 978 cm⁻¹ belongs to the trifluoromethyl group. -1 The peak at 724 cm⁻¹ is attributed to the CF bond; -1 The peak at that location is attributed to the out-of-plane bending of the aromatic -CH bonds.

[0079] Figure 6 The image shown is a comparison of the infrared spectra of crosslinkable fluorinated polyarylene ether containing allyl structure (UCL-PAE40) and crosslinked fluorinated polyarylene ether membrane material (CL-PAE40) in Example 4.

[0080] Test method: FTIR spectra (4000-400 cm⁻¹) were recorded on a Nicolet iS 50 Fourier transform infrared spectrometer manufactured by Thermo Fisher Scientific. -1 ).

[0081] Analysis: UCL-PAE40 at 1695cm -1 A vibrational absorption peak of the C=C bond appeared at this position. The absorption peak of the cross-linked polymer CL-PAE40 at this position has completely disappeared, indicating that the double bond has completely undergone cross-linking reaction after high-temperature thermosetting.

[0082] Figure 7 The graphs show the relationship between the dielectric constant and the electric field frequency of the crosslinkable fluorinated polyarylene ether films (UCL-PAE10-40) and crosslinked films (CL-PAE10-40) containing allyl structures in Examples 1-4.

[0083] Figure 8 This is the C1s XPS spectrum of the allyl-containing crosslinkable fluorinated polyarylene ether (UCL-PAE40) in Example 4;

[0084] Figure 9 This is the C1s XPS spectrum of the cross-linked fluorinated polyarylether membrane material (CL-PAE40) in Example 4.

[0085] pass Figure 8 and Figure 9Comparative analysis: For UCL-PAE40 before crosslinking, characteristic peaks are located at 292.3, 286.6, 284.8, and 284.2 eV, which are attributed to CF, COC, CC, and C=C bonds, respectively. The characteristic peak at 288.2 eV is attributed to the C=O bond, which may be due to the sample being exposed to air for a long time, resulting in CO2 adsorption on the surface. The disappearance of the C=C bond peak in the C1s core level spectrum of CL-PAE40 further indicates the success of crosslinking.

[0086] Test method: The elemental composition of the thin film surface was tested using a PHI 5000VersaProbe III X-ray photoelectron spectrometer.

[0087] Table 1. Molecular weights of crosslinkable fluorinated polyarylethers containing allyl groups.

[0088]

[0089]

[0090] Table 1 shows the number-average molecular weight, weight-average molecular weight, and polydispersity index (PDI) of allyl-containing crosslinkable fluorinated polyaryl ethers PAE10–40 dissolved in tetrahydrofuran. Table 1 lists the molecular weight data of PAE10–40 polyaryl ethers, with their number-average molecular weight values ​​ranging from 3.11 × 10⁴ to 4.02 × 10⁴ g / mol and their polydispersity indices ranging from 4.15 to 4.68, respectively. The results indicate that allyl-containing crosslinkable fluorinated polyaryl ethers with suitable molecular weights and molecular weight distributions were successfully prepared.

[0091] The molecular weight of the polymer was measured using a WATERS 515 gel permeation chromatography system. Tetrahydrofuran was used as the solvent, and the flow rate was 1.0 mL / min.

[0092] Table 2 Solubility

[0093]

[0094] Note: "++" indicates complete dissolution at room temperature; "+" indicates complete dissolution under heating conditions.

[0095] Dissolves; "+" indicates partial dissolution under heating; "-" indicates no dissolution under heating.

[0096] Dissolve.

[0097] Table 2 shows the solubility of crosslinkable fluorinated polyaryl ether membranes UCL-PAE10–40 and crosslinked fluorinated polyaryl ether membranes CL-PAE10–40. The solubility of 0.1 g of crosslinkable fluorinated polyaryl ethers containing allyl groups was determined by placing them in 10 mL of solvents (NMP, DMF, DMSO, THF, CHCl3, and Acetone). The crosslinkable fluorinated polyaryl ethers exhibited strong solubility in both strongly polar solvents (NMP, DMF, DMSO, and THF) and weakly polar solvents (CHCl3 and acetone). Before crosslinking, the large free volume of the fluorinated isopropyl and allyl groups disrupts the regularity of the polymer chains, increasing the distance between polymer molecular chains and reducing inter-chain interactions, thus resulting in strong solubility. The crosslinked fluorinated polyaryl ether membranes were all insoluble in solvents, which is attributed to the formation of the crosslinked network and indirectly proves the successful completion of the polymer crosslinking and curing reaction.

[0098] Table 3 Thermal properties

[0099]

[0100] Table 3 shows the thermal properties of crosslinkable fluorinated polyarylene ether membranes UCL-PAE10~40 and crosslinked fluorinated polyarylene ether membrane material CL-PAE10~40 with allyl structure.

[0101] T 5％ The temperature at which 5% weight loss occurs; T max T is the temperature at which the decomposition rate is at its maximum. g Glass transition temperature.

[0102] Thermogravimetric analysis (TGA) was performed on a TG 209F3 thermogravimetric analyzer. Tests were conducted under a nitrogen atmosphere with a heating rate of 20 °C / min and a temperature range of 50 °C to 800 °C. Glass transition temperatures were measured using a Perkin Elmer Pyris 1 differential scanning calorimeter. Tests were conducted under a nitrogen atmosphere with a heating rate of 10 °C / min and a temperature range of 50 °C to 300 °C.

[0103] Table 3 shows that the glass transition temperature of the uncrosslinked polymer film decreases with increasing 2,2'-diallylbisphenol A content. This is because increasing the 2,2'-diallylbisphenol A content increases the allyl group content of the polymer side chains, disrupting the regularity of the polymer chains, increasing the free volume, and thus lowering the glass transition temperature. Conversely, the glass transition temperature of the crosslinked fluorinated polyarylether film increases with increasing 2,2'-diallylbisphenol A content. This is because increasing the allyl group content increases the crosslinking network, significantly restricting the movement of polymer chain segments and increasing the glass transition temperature.

[0104] Table 3 shows that the T5% of both the pre- and post-crosslinking films decreases with increasing 2,2'-diallylbisphenol A content. Thermal stability mainly depends on the polymer backbone and side groups. Before crosslinking, the thermal stability of the allyl side chains is lower than that of the backbone containing rigid benzene rings; after crosslinking, the bond energy of the C / C bonds in the crosslinked network is lower than that of the backbone containing rigid benzene rings. Table 3 also shows that the T5% of UCL-PAE10, UCL-PAE20, UCL-PAE30, and UCL-PAE40 increased by 17, 42, 13, and 6 °C respectively after crosslinking, indicating that crosslinking can improve thermal stability. Furthermore, all samples exhibited maximum thermal decomposition temperatures above 550 °C and char residues above 50% at 800 °C, demonstrating excellent thermal performance.

[0105] Table 4 Mechanical Properties

[0106]

[0107] Table 4 shows the mechanical properties of crosslinkable fluorinated polyarylene ethers UCL-PAE10~40 and crosslinked films CL-PAE10~40 containing allyl structures.

[0108] Stress-strain curves were obtained from a WDT-10 electronic universal testing machine. Mechanical properties were evaluated using these curves. The film was cut into 5cm × 1cm pieces. The tensile rate was 5mm / min during testing, and the experiment was repeated 5 times, with the average value taken.

[0109] As shown in Table 4, the crosslinking network improves the rigidity of the crosslinked fluorinated polyarylene ether film chain, resulting in a lower elongation at break after crosslinking compared to the uncrosslinked film. This elongation decreases further with increasing crosslinking network content, from 6.8% to 4.3%. The tensile strength and tensile modulus of all allyl-containing crosslinkable fluorinated polyarylene ether films improved after crosslinking, thanks to the formation of the crosslinking network. Furthermore, the tensile strength and tensile modulus of the crosslinked film (CL-PAEn) initially increased and then decreased with increasing allyl content. The improved mechanical properties are attributed to the high-temperature crosslinking reaction, while the decreased properties are attributed to over-crosslinking. Notably, CL-PAE20 exhibited the best mechanical properties, with a tensile strength of 146.7 MPa and a tensile modulus of 4.5 GPa. This demonstrates that moderate crosslinking improves mechanical properties, while excessive crosslinking increases material brittleness, thus reducing mechanical properties.

[0110] Table 5 Dielectric properties and water absorption rate

[0111]

[0112] Table 5 shows the dielectric properties and water absorption rates of crosslinkable fluorinated polyaryl ethers UCL-PAE10~40 and crosslinked fluorinated polyaryl ether membrane materials CL-PAE10~40 with allyl structures.

[0113] The dielectric constant and dielectric loss were tested using a TH2826 LCR digital bridge. The tests were conducted at room temperature, with a frequency range of 10Hz-10Hz. 6 Hz.

[0114] After immersing the film in deionized water for a certain period of time, the water absorption rate is obtained according to the formula: W=(m2-m1) / m1×100%, where W is the water absorption rate, m1 is the weight of the sample when it is dry, and m2 is the weight of the sample after immersing it in water for a certain period of time.

[0115] Table 5 shows that the dielectric constant of the uncrosslinked allyl-containing crosslinkable fluorinated polyaryl ether film at 1 MHz ranges from 2.47 to 2.97, increasing with increasing 2,2'-diallylbisphenol A content. This is because increasing 2,2'-diallylbisphenol A content decreases fluorine content, increases electronic polarizability, and thus increases the dielectric constant. Conversely, the dielectric constant of the crosslinked fluorinated polyaryl ether film decreases with increasing 2,2'-diallylbisphenol A content, ranging from 1.93 to 2.24 at 1 MHz. The crosslinked network structure restricts polymer segment migration, reduces dipole orientation, limits the polarization of the polymer electron cloud under an applied electric field, and also restricts the orientation of polymer segments in the direction of the external electric field. Therefore, the dielectric constant of the crosslinked film is lower than that of the uncrosslinked film; at 1 MHz, CL-PAE40 has the lowest dielectric constant, only 1.93.

[0116] The various embodiments of the present invention have been described above. These descriptions are exemplary and not exhaustive, nor are they limited to the disclosed embodiments. Many modifications and variations will be apparent to those skilled in the art without departing from the scope and principles of the described embodiments, and these modifications and variations should also be considered within the scope of protection of the present invention.

Claims

1. A method for preparing a cross-linked fluorinated polyarylether membrane material, characterized in that, The molecular formula of the cross-linked fluorinated polyarylether membrane material is shown in Formula 1: ， Formula 1 In the structural formula 1, the content of x = 0.1–0.4, 1–x = 0.6–0.9, and n = 40–70. The specific steps are as follows: Step (1) Preparation of crosslinkable fluorinated polyarylene ethers containing allyl structures: Perfluorobiphenyl, bisphenol AF, 2,2'-diallylbisphenol A, potassium carbonate and N 2-Methyl-2-pyrrolidone was added to a three-necked flask equipped with a mechanical stirrer, a water condenser, and a nitrogen inlet and outlet and stirred to react. After the reaction was completed, a viscous polymer solution was obtained. The polymer solution was slowly poured into ethanol to settle. After filtration, washing and drying, fibrous allyl-containing crosslinkable fluorinated polyarylene ether was obtained. Step (2) Preparation of crosslinkable fluorinated polyaryl ether films containing allyl structures: The polyaryl ether obtained in step (1) is heated and fully dissolved in... N The film was prepared by filtering the methyl-2-pyrrolidone mixture through a sintered glass funnel to obtain a homogeneous solution. This solution was then cast onto a glass substrate, dried in an oven, and allowed to cool naturally. The film was then peeled off the glass substrate to obtain a crosslinkable fluorinated polyarylene film containing an allyl structure. Step (3) Preparation of cross-linked fluorinated polyarylene ether membrane material: The cross-linkable fluorinated polyarylene ether membrane with allyl structure obtained in step (2) is vacuum dried at high temperature and cross-linked to obtain cross-linked fluorinated polyarylene ether membrane material.

2. The method for synthesizing the cross-linked fluorinated polyarylether membrane material as described in claim 1, characterized in that, In step (1), the molar amount of the perfluorobiphenyl is equal to the sum of the molar amounts of 2,2'-diallylbisphenol A and bisphenol AF, and the molar ratio of 2,2'-diallylbisphenol A to bisphenol AF is 1:9 to 4:

6.

3. The method for synthesizing the cross-linked fluorinated polyarylether membrane material as described in claim 2, characterized in that, In step (1), the molar amount of potassium carbonate is 1 to 2 times the molar amount of perfluorobiphenyl.

4. The method for synthesizing a cross-linked fluorinated polyarylether membrane material as described in claim 2, characterized in that, In step (1), the N The amount of 2-methyl-2-pyrrolidone used is 3 to 5 times the total mass of perfluorobiphenyl, bisphenol AF and 2,2'-diallylbisphenol A.

5. The method for synthesizing a cross-linked fluorinated polyarylether membrane material as described in claim 2, characterized in that, In step (1), the reaction conditions are: reaction temperature 100~120℃, reaction time 4~6 hours.

6. The method for synthesizing a cross-linked fluorinated polyarylether membrane material as described in claim 2, characterized in that, In step (2), the drying conditions of the oven are: drying at 80℃, 100℃, 120℃, 140℃, 160℃, 180℃, and 200℃ for 2 hours respectively.

7. The method for synthesizing a cross-linked fluorinated polyarylether membrane material as described in claim 2, characterized in that, In step (2), the N The amount of methyl-2-pyrrolidone used is 10-15 times the amount of crosslinkable fluorinated polyarylene ethers containing allyl structures.

8. The method for synthesizing a cross-linked fluorinated polyarylether membrane material as described in claim 2, characterized in that, In step (3), the crosslinking conditions are: under vacuum, at a temperature of 250~260℃.

9. An application of a cross-linked fluorinated polyarylether membrane material obtained by the preparation method as described in claim 1, characterized in that, The cross-linked fluorinated polyarylether membrane material can be used as a membrane material in the fields of communication and microelectronics.

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