Crosslinked polyarylether membrane material containing bismaleimide structure as well as preparation method and application of crosslinked polyarylether membrane material

Abstract

The invention belongs to the technical field of organic membrane materials, and particularly relates to a cross-linked polyarylether membrane material containing a bismaleimide structure as well as a preparation method and application of the cross-linked polyarylether membrane material. The cross-linked polyarylether membrane material containing the bismaleimide structure provided by the invention has a structure as shown in a formula 1: # imgabs0 #, x is any numerical value in the range of 0.4-0.6, and n is any integer in the range of 60-80. A fluorine-containing structure is introduced into the polyarylether, so that the polarizability of the polyarylether is reduced; meanwhile, by introducing a bismaleimide structure, olefin double bonds in the bismaleimide structure are subjected to ring opening to obtain a cross-linked polymer, so that the dielectric constant is reduced, and the thermal stability, the mechanical property and the dielectric property of the cross-linked polymer are improved; the movement of the chain segment is limited by introducing the cross-linked network, and the dielectric constant is further reduced. The cross-linked polyarylether membrane material containing the bismaleimide structure has excellent thermal stability and good dielectric property, and can be used as a low dielectric material in the field of microelectronics in an environment with a relatively high processing temperature.

Description

Technical Field

[0001] The present invention belongs to the technical field of organic membrane materials, and particularly relates to a crosslinked polyarylether membrane material containing a bismaleimide structure, a preparation method thereof, and an application thereof. Background Art

[0002] In the microelectronics field, with the improvement of integration and the reduction of feature size, problems such as resistance-capacitance (RC) delay, crosstalk, and additional power consumption of signals have become increasingly serious. Therefore, it has become increasingly crucial to use low-dielectric-constant interlayer dielectric materials to alleviate these problems.

[0003] Existing low-dielectric-constant materials are mainly divided into three categories: inorganic materials, organic / inorganic hybrid materials, and organic polymer materials; among these materials, compared with traditional inorganic dielectric materials, organic polymer materials usually exhibit lower dielectric constants, and organic polymer materials show significant advantages in the design of chemical composition and geometric structure, making them have great potential as insulating layer materials in the microelectronics field.

[0004] However, organic polymer materials also have some defects that cannot be ignored, such as poor heat resistance and insufficient thermal stability, which limit their application in environments that require relatively high processing temperatures. Therefore, it is imperative to develop a new material that has both excellent dielectric properties and mechanical properties, as well as good thermal stability and processing properties. Summary of the Invention

[0005] In view of this, the present invention provides a crosslinked polyarylether membrane material containing a bismaleimide structure, a preparation method thereof, and an application thereof. The crosslinked polyarylether membrane material containing a bismaleimide structure provided by the present invention has excellent dielectric properties, mechanical properties, good thermal stability, and processability, expanding its application fields as a low-dielectric material.

[0006] In order to solve the above technical problems, the present invention provides a crosslinked polyarylether membrane material containing a bismaleimide structure, having the structure shown in Formula 1:

[0007]

[0008] Wherein, x is any value from 0.4 to 0.6, and n is any integer from 60 to 80.

[0009] The present invention also provides a preparation method of the crosslinked polyarylether membrane material containing a bismaleimide structure described in the above technical solution, including the following steps:

[0010] 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane, 2,2-bis(4-hydroxyphenyl)hexafluoropropane, perfluorobiphenyl, anhydrous potassium carbonate and N,N-dimethylacetamide are first mixed and then subjected to an aromatic nucleophilic substitution reaction to obtain Compound 1;

[0011] Compound 1, maleic anhydride and N-methyl-2-pyrrolidone are second mixed and then third mixed with a catalyst and a dehydrating agent for a dehydration cyclization reaction to obtain Compound 2;

[0012] Compound 2 is dissolved in N-methyl-2-pyrrolidone and then subjected to molding and thermal curing in sequence to obtain the crosslinked polyarylether membrane material containing a bismaleimide structure;

[0013] Compound 1 has the structure shown in Formula 2, and Compound 2 has the structure shown in Formula 3:

[0014]

[0015] Preferably, the molar ratio of 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane to 2,2-bis(4-hydroxyphenyl)hexafluoropropane is 4:6 to 6:4;

[0016] The total molar amount of 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane and 2,2-bis(4-hydroxyphenyl)hexafluoropropane and the molar ratio of perfluorobiphenyl is 1:1;

[0017] The molar ratio of the anhydrous potassium carbonate to perfluorobiphenyl is 1 to 2:1;

[0018] The mass ratio of the total mass of 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane, 2,2-bis(4-hydroxyphenyl)hexafluoropropane and perfluorobiphenyl to N,N-dimethylacetamide is 1:3.5 to 6.

[0019] Preferably, the temperature of the aromatic nucleophilic substitution reaction is 80 to 90 °C and the time is 4 to 5 h.

[0020] Preferably, Compound 1 includes an amino-containing structural unit, and the amino-containing structural unit is

[0021] The molar amount of maleic anhydride used is 2 to 2.1 times the molar number of the amino-containing structural unit in Compound 1;

[0022] The mass ratio of the total mass of Compound 1 and maleic anhydride to N-methyl-2-pyrrolidone is 0.05 to 0.15:1;

[0023] The catalyst includes triethylamine, and the molar amount of the catalyst used is 3 to 4 times the molar number of the amino-containing structural unit in Compound 1;

[0024] The dehydrating agent includes acetic anhydride, and the molar amount of the dehydrating agent is 3 to 4 times the molar number of the amino group-containing structural unit in Compound 1.

[0025] Preferably, the temperature of the dehydration cyclization reaction is 90 to 100 °C, and the time is 6 to 8 h.

[0026] Preferably, the forming is to dissolve Compound 2 in N-methyl-2-pyrrolidone and then filter, and cast the obtained filtrate in a mold and then dry.

[0027] Preferably, the mass ratio of N-methyl-2-pyrrolidone to Compound 2 used for forming is 8.5 to 15:1;

[0028] The drying procedure is to keep warm at 80 °C, 100 °C, 120 °C, 140 °C, 160 °C, 180 °C and 200 °C for 2 h in sequence.

[0029] Preferably, the temperature of the thermal curing is 270 to 280 °C, and the time is 2 to 4 h.

[0030] The present invention also provides the application of the bismaleimide structure-containing crosslinked polyarylether membrane material described in the above technical solution or the bismaleimide structure-containing crosslinked polyarylether membrane material prepared by the preparation method described in the above technical solution as a low dielectric material in microelectronics.

[0031] The bismaleimide structure-containing crosslinked polyarylether membrane material provided by the present invention has the structure shown in Formula 1: Formula 1; wherein, x is any value from 0.4 to 0.6, and n is any integer from 60 to 80. The present invention reduces its polarizability by introducing fluorine-containing structures (trifluoroisopropyl and perfluorobiphenyl) into the polyarylether; at the same time, by introducing a bismaleimide structure, the olefin double bond in it is ring-opened to obtain a crosslinked polymer, thereby reducing the dielectric constant and improving its thermal stability, mechanical properties and dielectric properties; and the present invention further reduces the dielectric constant by introducing a crosslinked network to limit the segment motion. The bismaleimide structure-containing crosslinked polyarylether membrane material provided by the present invention has both excellent thermal stability and good dielectric properties, and can be used as a low dielectric material in the microelectronics field in an environment with a relatively high processing temperature. BRIEF DESCRIPTION OF THE DRAWINGS

[0032] Figure 1 It is a schematic reaction flow diagram for preparing the bismaleimide structure-containing crosslinked polyarylether membrane material in Examples 1 to 3;

[0033] Figure 2 For the 1 1H NMR spectrum of the amino group-containing fluorinated polyarylether (FPAE-50) in Example 2;

[0034] Figure 3 1H NMR spectrum of fluorinated polyarylether (FPAE-50-PI) incorporating bismaleimide in Example 2 1 1H NMR spectrum

[0035] Figure 4 Infrared spectra of fluorinated polyarylether film with amino structure (50FPAE), fluorinated polyarylether film incorporating bismaleimide (50FPAE-PI), and crosslinked fluorinated polyarylether membrane material incorporating cured bismaleimide (CL-50FPAE-PI) prepared in Example 2

[0036] Figure 5 Partial infrared spectra of fluorinated polyarylether film with amino structure (50FPAE), fluorinated polyarylether film incorporating bismaleimide (50FPAE-PI), and crosslinked fluorinated polyarylether membrane material incorporating cured bismaleimide (CL-50FPAE-PI) in Example 2

[0037] Figure 6 Relationship diagrams of dielectric constant and dielectric loss with the change of electric field frequency for fluorinated polyarylether film with amino structure (50FPAE) and crosslinked fluorinated polyarylether membrane material incorporating cured bismaleimide (CL-50FPAE-PI) in Example 2 Detailed implementation manners

[0038] The present invention provides a crosslinked polyarylether membrane material containing a bismaleimide structure, having the structure shown in Formula 1:

[0039]

[0040] Wherein, x is any value from 0.4 to 0.6, specifically 0.4, 0.5 or 0.6; n is any integer from 60 to 80, and can also be any integer from 65 to 75.

[0041] The present invention also provides a preparation method of the crosslinked polyarylether membrane material containing a bismaleimide structure described in the above technical solution, including the following steps:

[0042] Mix 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane, 2,2-bis(4-hydroxyphenyl)hexafluoropropane, perfluorobiphenyl, anhydrous potassium carbonate and N,N-dimethylacetamide for the first time and carry out aromatic nucleophilic substitution reaction to obtain Compound 1;

[0043] Mix the Compound 1, maleic anhydride and N-methyl-2-pyrrolidone for the second time and then mix with a catalyst and a dehydrating agent for the third time to carry out dehydration cyclization reaction to obtain Compound 2;

[0044] Dissolve the compound 2 in N-methyl-2-pyrrolidone, followed by shaping and thermal curing to obtain the crosslinked polyarylether membrane material containing a bismaleimide structure.

[0045] The compound 1 has the structure shown in Formula 2, and the compound 2 has the structure shown in Formula 3:

[0046]

[0047] In the present invention, 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane, 2,2-bis(4-hydroxyphenyl)hexafluoropropane, perfluorobiphenyl, anhydrous potassium carbonate and N,N-dimethylacetamide are first mixed and then subjected to an aromatic nucleophilic substitution reaction to obtain compound 1. As a specific embodiment of the present invention, the molar ratio of 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane to 2,2-bis(4-hydroxyphenyl)hexafluoropropane can be 4:6 to 6:4, specifically 4:6, 5:5 or 6:4. The present invention controls the value of x by adjusting the molar ratio of 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane to 2,2-bis(4-hydroxyphenyl)hexafluoropropane.

[0048] As a specific embodiment of the present invention, the total molar amount of 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane and 2,2-bis(4-hydroxyphenyl)hexafluoropropane to the molar ratio of perfluorobiphenyl can be 1:1; the molar ratio of anhydrous potassium carbonate to perfluorobiphenyl can be 1 to 2:1, specifically 1.3:1, 1.6:1 or 1.8:1; the mass ratio of the total mass of 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane, 2,2-bis(4-hydroxyphenyl)hexafluoropropane and perfluorobiphenyl to N,N-dimethylacetamide can be 1:3.5 to 6, specifically 1:3.6, 1:4, 1:4.5, 1:5, 1:5.5 or 1:6. In the present invention, the N,N-dimethylacetamide is a solvent. Selecting a solvent with weaker solubility than N,N-dimethylacetamide will cause insufficient dissolution of the system and insufficient reaction; selecting a solvent with stronger solubility than N,N-dimethylacetamide (such as N-methyl-2-pyrrolidone), the resulting polymer film will not be completely transparent after casting.

[0049] In the present invention, the anhydrous potassium carbonate is a reaction catalyst.

[0050] The present invention has no special requirements for the first mixing, as long as the mixture can be evenly mixed. As a specific embodiment of the present invention, the temperature of the aromatic nucleophilic substitution reaction can be 80-90 °C, specifically 80 °C, 85 °C or 90 °C; the time of the aromatic nucleophilic substitution reaction can be 4-5 h, specifically 4 h, 4.5 h or 5 h. The present invention can provide the temperature required for the aromatic nucleophilic substitution reaction by means of oil bath heating. As a specific embodiment of the present invention, the aromatic nucleophilic substitution reaction can be carried out under a protective atmosphere, and the protective atmosphere can be nitrogen; the aromatic nucleophilic substitution reaction can be accompanied by stirring, and the present invention has no special limitation on the stirring, as long as the reaction can be fully carried out.

[0051] As a specific embodiment of the present invention, after the aromatic nucleophilic substitution reaction, it may further include: mixing the system after the aromatic nucleophilic substitution reaction and ethanol, and performing sedimentation and filtration in sequence, washing and drying the solid obtained by filtration in sequence to obtain the compound 1. The present invention has no special limitation on the dosage of the ethanol, and it can be carried out in a conventional manner in the art. The present invention has no special requirements for the filtration, and a conventional method in the art can be used. As a specific embodiment of the present invention, the washing can be water washing; the present invention has no special requirements for the drying, as long as the solvent on the surface of the solid can be removed.

[0052] In the present invention, the compound 1 is a fluorinated polyarylether containing an amino structure, the compound 1 includes an amino structure unit, and the amino structure unit is

[0053] After obtaining the compound 1, the present invention mixes the compound 1, maleic anhydride and N-methyl-2-pyrrolidone for the second time and then mixes them with a catalyst and a dehydrating agent for the third time to carry out a dehydration cyclization reaction to obtain the compound 2. As a specific embodiment of the present invention, the molar dosage of maleic anhydride ( ) can be 2-2.1 times the molar number of the amino structure unit in the compound 1; the mass ratio of the total mass of the compound 1 and maleic anhydride to the mass of N-methyl-2-pyrrolidone can be 0.05-0.15:1, or can also be 0.08-0.13:1. In the present invention, N-methyl-2-pyrrolidone has a high solubility for the compound 1, and the obtained solution of the compound 1 has a low viscosity, which is convenient for subsequent reactions.

[0054] As a specific embodiment of the present invention, the second mixing can be carried out under a protective atmosphere, and the protective atmosphere can be nitrogen; the second mixing can be carried out under stirring conditions, and the stirring time can be 12 to 24 hours, or can also be 15 to 20 hours; the stirring temperature can be room temperature, and the temperature of the room temperature can be 20 to 35 °C, or can also be 25 to 30 °C. Through the second mixing of the present invention, a polyamic acid structure will be formed.

[0055] As a specific embodiment of the present invention, the catalyst can include triethylamine, and the molar amount of the catalyst can be 3 to 4 times the molar number of the amino group-containing structural unit in Compound 1; the dehydrating agent can include acetic anhydride, and the molar amount of the dehydrating agent can be 3 to 4 times the molar number of the amino group-containing structural unit in Compound 1.

[0056] The present invention has no special requirements for the third mixing, as long as it can be mixed evenly. As a specific embodiment of the present invention, the temperature of the dehydration cyclization reaction can be 90 to 100 °C, specifically 90 °C, 95 °C or 100 °C; the time of the dehydration cyclization reaction can be 6 to 8 hours, specifically 6 hours, 6.5 hours, 7 hours, 7.5 hours or 8 hours. The present invention can adopt an oil bath heating method to provide the temperature required for the dehydration cyclization reaction. As a specific embodiment of the present invention, the dehydration cyclization reaction can be carried out under a protective atmosphere, and the protective atmosphere can be nitrogen.

[0057] As a specific embodiment of the present invention, after the dehydration cyclization reaction, it can also include: mixing the system after the dehydration cyclization reaction with an aqueous solution of methanol for sedimentation, and after filtration, washing and drying the obtained solid in sequence to obtain Compound 2. As a specific embodiment of the present invention, the mass concentration of the aqueous solution of methanol can be 50 to 60%, or can also be 55 to 58%. The present invention has no special limitation on the dosage of the aqueous solution of methanol, and it can be carried out in a conventional manner in the art. The present invention has no special requirements for the filtration, and a conventional method in the art can be adopted. As a specific embodiment of the present invention, the washing can be water washing; the present invention has no special requirements for the drying, as long as the solvent on the surface of the solid can be removed.

[0058] In the present invention, Compound 2 is a fluorinated polyarylether introduced with bismaleimide.

[0059] After obtaining Compound 2, the present invention dissolves the Compound 2 in N-methyl-2-pyrrolidone and then performs molding and thermal curing in sequence to obtain the crosslinked polyarylether membrane material containing a bismaleimide structure. As a specific embodiment of the present invention, the molding can be to dissolve Compound 2 in N-methyl-2-pyrrolidone and then filter, and cast the filtrate obtained by the filtration in a mold and then dry. As a specific embodiment of the present invention, the mass ratio of N-methyl-2-pyrrolidone to Compound 2 used for molding can be 8.5 to 15:1, specifically 9:1, 10:1, 11:1, 12:1, 13:1, 13.5:1, 14:1 or 15:1; the temperature of the dissolution can be 50 to 60 °C, and can also be 55 to 60 °C; the material of the mold can be glass. As a specific embodiment of the present invention, the filtration can be carried out using a sintered glass funnel; the drying can be drying by baking, and the baking procedure can be to keep warm at 80 °C, 100 °C, 120 °C, 140 °C, 160 °C, 180 °C and 200 °C for 2 h in sequence. The present invention can remove the solvent after drying.

[0060] As a specific embodiment of the present invention, the temperature of the thermal curing can be 270 to 280 °C, specifically 270 °C, 275 °C or 280 °C; the time of the thermal curing can be 2 to 4 h, specifically 2 h, 3 h or 4 h.

[0061] The fluorinated polyarylether containing an amino structure provided by the present invention improves the fluorine content of the system and reduces the dielectric constant of the system by introducing trifluoroisopropyl and perfluorobiphenyl structures; and by introducing amino groups that can react with acid anhydrides, it enhances the flexibility of the polymer molecular structure design; the fluorinated polyarylether containing bismaleimide prepared by the present invention has crosslinking sites in the molecular structure by introducing a bismaleimide structure and can undergo a crosslinking reaction; the crosslinked polyarylether membrane material containing cured bismaleimide prepared by the present invention restricts the segment motion and reduces the dielectric constant by introducing a crosslinked network.

[0062] The present invention also provides the application of the crosslinked polyarylether membrane material containing a bismaleimide structure described in the above technical solution or the crosslinked polyarylether membrane material containing a bismaleimide structure prepared by the preparation method described in the above technical solution as a low dielectric material in microelectronics. The crosslinked polyarylether membrane material containing a bismaleimide structure provided by the present invention has excellent comprehensive properties such as dielectric properties, thermal properties and mechanical properties, and has potential application value in the microelectronics field.

[0063] In order to further illustrate the present invention, the technical solutions provided by the present invention will be described in detail below in conjunction with embodiments, but they cannot be understood as limiting the protection scope of the present invention.

[0064] The sources of the drugs and reagents in the examples are as follows:

[0065] Maleic anhydride: Shanghai Lingfeng Chemical Reagent Co., Ltd., purity ≥ 99.5%;

[0066] Triethylamine (TEA): Shanghai Lingfeng Chemical Reagent Co., Ltd., purity ≥ 99%;

[0067] Acetic anhydride (Ac 2 O): Sinopharm Chemical Reagent Co., Ltd., purity ≥ 98.5%;

[0068] 2,2-Bis(4-hydroxyphenyl)hexafluoropropane (bisphenol AF): Tokyo Chemical Industry Co., Ltd., purity > 98%;

[0069] 2,2-Bis(3-amino-4-hydroxyphenyl)hexafluoropropane: Tokyo Chemical Industry Co., Ltd., purity > 98%;

[0070] Perfluorobiphenyl: Wuhan Changcheng Huacheng Technology Development Co., Ltd., purity > 98%;

[0071] Anhydrous potassium carbonate (K 2 CO 3 ): Shanghai Lingfeng Chemical Reagent Co., Ltd., purity ≥ 99%;

[0072] N,N-Dimethylacetamide (DMAc): Shanghai Lingfeng Chemical Reagent Co., Ltd., purity ≥ 98%;

[0073] N-Methyl-2-pyrrolidone (NMP): Shanghai Lingfeng Chemical Reagent Co., Ltd., purity ≥ 99%.

[0074] Example 1

[0075] Step (1) Preparation of fluorinated polyarylether with amino structure (FPAE-40)

[0076] Add 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane (1.7580 g, 4.8 mmol), 2,2-bis(4-hydroxyphenyl)hexafluoropropane (2.4208 g, 7.2 mmol), perfluorobiphenyl (4.0093 g, 12 mmol), anhydrous potassium carbonate (2.6536 g, 19.2 mmol), and N,N-dimethylacetamide (32 mL) into a three-necked flask (equipped with nitrogen inlet and outlet, spherical condenser and mechanical stirrer), and carry out an aromatic nucleophilic substitution reaction for 5 h under a nitrogen atmosphere and an 80 °C oil bath. After the reaction, precipitate in ethanol, filter, wash, and dry to obtain a fluorinated polyarylether with amino structure, denoted as FPAE-40.

[0077] Step (2) Preparation of fluorinated polyarylether with bismaleimide introduced (FPAE-40-PI)

[0078] The amino group-containing fluorinated polyarylether obtained in step (1) (0.6424 g, 1 mmol) was added to a three-necked flask equipped with nitrogen inlet and outlet and a mechanical stirrer, and was completely dissolved with N-methyl-2-pyrrolidone (10 mL). Maleic anhydride (0.0784 g, 0.8 mmol) was added at room temperature (30 °C), and the mixture was stirred overnight (24 h) under a nitrogen atmosphere and at room temperature (30 °C). Then, a condensing device was equipped for the three-necked flask, and triethylamine (0.1214 g, 1.2 mmol) and acetic anhydride (0.1225 g, 1.2 mmol) were added to the flask. A dehydration cyclization reaction was carried out for 6 h under a nitrogen atmosphere and an oil bath heating condition at 90 °C. After the reaction was completed, it was precipitated in an aqueous solution of methanol with a mass concentration of 55%, filtered, washed, and dried to obtain a powdery fluorinated polyarylether incorporating bismaleimide, denoted as FPAE-40-PI.

[0079] Preparation of crosslinked fluorinated polyarylether membrane material (CL-40FPAE-PI) incorporating cured bismaleimide in step (3)

[0080] The amino group-containing fluorinated polyarylether incorporating bismaleimide obtained in step (2) (0.2 g) was dissolved in N-methyl-2-pyrrolidone (3 mL) at a temperature of 50 °C, filtered through a fritted funnel, and cast on a glass mold. The solvent was dried in an oven, and the drying procedure was to dry at 80 °C, 100 °C, 120 °C, 140 °C, 160 °C, 180 °C, and 200 °C for 2 h in sequence. The dried membrane was thermally cured at 280 °C for 2 h to obtain a crosslinked polyarylether membrane material containing a bismaleimide structure, denoted as CL-40FPAE-PI.

[0081] Example 2

[0082] Preparation of amino group-containing fluorinated polyarylether (FPAE-50) in step (1)

[0083] 2,2-Bis(3-amino-4-hydroxyphenyl)hexafluoropropane (2.1975 g, 6 mmol), 2,2-bis(4-hydroxyphenyl)hexafluoropropane (2.0173 g, 6 mmol), perfluorobiphenyl (4.0093 g, 12 mmol), anhydrous potassium carbonate (2.6536 g, 19.2 mmol), and N,N-dimethylacetamide (32 mL) were added to a three-necked flask (this three-necked flask was equipped with nitrogen inlet and outlet, a spherical condenser, and a mechanical stirrer). An aromatic nucleophilic substitution reaction was carried out for 5 h under a nitrogen atmosphere and an oil bath heating condition at 80 °C. After the reaction was completed, it was precipitated in ethanol, filtered, washed, and dried to obtain an amino group-containing fluorinated polyarylether, denoted as FPAE-50.

[0084] Preparation of fluorinated polyarylether containing bismaleimide (FPAE-50-PI) in step (2)

[0085] Add the fluorinated polyarylether containing amino structure obtained in step (1) (0.6454 g, 1 mmol) into a three-necked flask equipped with nitrogen inlet and outlet and a mechanical stirrer, dissolve it thoroughly with N-methyl-2-pyrrolidone (10 mL), add maleic anhydride (0.0981 g, 1 mmol) at room temperature (30 °C), and stir overnight (24 h) under a nitrogen atmosphere and at room temperature (30 °C); then equip the three-necked flask with a condensing device, add triethylamine (0.1518 g, 1.5 mmol) and acetic anhydride (0.1531 g, 1.5 mmol) into the flask, and carry out a 6-h dehydration cyclization reaction under a nitrogen atmosphere and an oil bath heating condition of 90 °C. After the reaction is completed, precipitate in an aqueous solution of methanol with a mass concentration of 55%, filter, wash, and dry to obtain a powdery fluorinated polyarylether containing bismaleimide, denoted as FPAE-50-PI.

[0086] Preparation of crosslinked fluorinated polyarylether membrane material containing cured bismaleimide (CL-50FPAE-PI) in step (3)

[0087] Dissolve the fluorinated polyarylether containing bismaleimide obtained in step (2) (0.2 g) in N-methyl-2-pyrrolidone (3 mL) at a temperature of 55 °C, filter through a sintered glass funnel, and then cast it on a glass mold. Dry the solvent in an oven, and the drying procedure is to dry at 80 °C, 100 °C, 120 °C, 140 °C, 160 °C, 180 °C, and 200 °C for 2 h in sequence; thermally cure the dried membrane at 280 °C for 2 h to obtain a crosslinked polyarylether membrane material containing bismaleimide structure, denoted as CL-50FPAE-PI (for infrared detection).

[0088] Example 3

[0089] Preparation of fluorinated polyarylether containing amino structure (FPAE-60) in step (1)

[0090] Add 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane (2.6371 g, 7.2 mmol), 2,2-bis(4-hydroxyphenyl)hexafluoropropane (1.6139 g, 4.8 mmol), perfluorobiphenyl (4.0093 g, 12 mmol), anhydrous potassium carbonate (2.6536 g, 19.2 mmol), and N,N-dimethylacetamide (32 mL) into a three-necked flask (equipped with nitrogen inlet and outlet, a spherical condenser, and a mechanical stirrer), and carry out an aromatic nucleophilic substitution reaction under a nitrogen atmosphere and an oil bath heating condition of 80 °C for 5 h. After the reaction is completed, precipitate in ethanol, filter, wash, and dry to obtain a fluorinated polyarylether containing amino structure, denoted as FPAE-60.

[0091] Preparation of fluorinated polyarylether containing bismaleimide (FPAE-60-PI) in step (2)

[0092] Add the fluorinated polyarylether containing amino structure obtained in step (1) (0.6484 g, 1 mmol) into a three-necked flask equipped with nitrogen inlet and outlet and a mechanical stirrer, dissolve it thoroughly with N-methyl-2-pyrrolidone (10 mL), add maleic anhydride (0.1177 g, 1.2 mmol) at room temperature (30 °C), and stir overnight (24 h) under a nitrogen atmosphere and at room temperature (30 °C); then equip the three-necked flask with a condensing device, add triethylamine (0.1821 g, 1.8 mmol) and acetic anhydride (0.1838 g, 1.8 mmol) into the flask, and carry out a 6-h dehydration cyclization reaction under a nitrogen atmosphere and at an oil bath temperature of 90 °C. After the reaction is completed, precipitate in an aqueous solution of methanol with a mass concentration of 55%, filter, wash, and dry to obtain a powdery fluorinated polyarylether containing bismaleimide, denoted as FPAE-60-PI.

[0093] Preparation of crosslinked fluorinated polyarylether membrane material containing cured bismaleimide (CL-60FPAE-PI) in step (3)

[0094] Dissolve the fluorinated polyarylether containing bismaleimide obtained in step (2) (0.2 g) in N-methyl-2-pyrrolidone (3 mL) at a temperature of 50 °C, filter it through a sintered glass funnel and pour it onto a glass mold, dry the solvent in an oven, and the drying procedure is to dry for 2 h at 80 °C, 100 °C, 120 °C, 140 °C, 160 °C, 180 °C, and 200 °C in sequence; heat-cure the dried membrane at 280 °C for 2 h to obtain a crosslinked polyarylether membrane material containing bismaleimide structure, denoted as CL-60FPAE-PI.

[0095] The reaction processes for preparing the crosslinked polyarylether membrane materials containing bismaleimide structure in Examples 1 to 3 are as Figure 1 shown.

[0096] Perform 1 1H nuclear magnetic resonance detection (using an AVANCE III 400M digital nuclear magnetic resonance spectrometer produced by Bruker with CDCl 3 as the solvent) on the FPAE-50 and FPAE-50-PI prepared in Example 2 to obtain 1 1HNMR spectra, as Figure 2 , 3 shown, where Figure 2 is the 1 1HNMR spectrum of FPAE-50, Figure 3 is the1 HNMR spectrum. Figure 2 The chemical shifts in the range of 6.50 - 7.75 ppm belong to the protons on the benzene ring; the chemical shift at 4.05 ppm is attributed to the characteristic peak of the amino group. Figure 3 The chemical shifts in the range of 6.75 - 7.75 ppm belong to the protons on the benzene ring; the characteristic peak of the amino group at 4.05 ppm disappears, and the signal of vinyl protons appears at 6.54 ppm, indicating the successful introduction of bismaleimide.

[0097] The fluorinated polyarylether film containing amino structure was prepared according to the following method:

[0098] Dissolve the fluorinated polyarylether containing amino structure obtained in step (1) of Example 2 (0.2 g) in N-methyl-2-pyrrolidone (3 mL) at a temperature of 55 °C, filter through a sintered glass funnel, pour it onto a glass mold, and dry the solvent in an oven. The drying procedure is to dry at 80 °C, 100 °C, 120 °C, 140 °C, 160 °C, 180 °C, and 200 °C for 2 h in sequence; cool naturally to 30 °C, and peel off the film to obtain the fluorinated polyarylether film containing amino structure (denoted as FPAE-50) for infrared characterization.

[0099] The fluorinated polyarylether film incorporating bismaleimide was prepared according to the following method:

[0100] Dissolve the fluorinated polyarylether incorporating bismaleimide obtained in step (2) of Example 2 (0.2 g) in N-methyl-2-pyrrolidone (3 mL) at a temperature of 55 °C, filter through a sintered glass funnel, pour it onto a glass mold, and dry the solvent in an oven. The drying procedure is to dry at 80 °C, 100 °C, 120 °C, 140 °C, 160 °C, 180 °C, and 200 °C for 2 h in sequence; cool naturally to 30 °C, and peel off the film to obtain the fluorinated polyarylether film incorporating bismaleimide (denoted as 50FPAE-PI) for infrared characterization.

[0101] Perform infrared detection on 50FPAE, 50FPAE-PI, and CL-50FPAE-PI prepared in Example 2 (record the FTIR spectrum at 4000 - 400 cm on a Nicolet iS 50 Fourier transform infrared spectrometer produced by Thermo Fisher Scientific) -1 ), and obtain the infrared spectra as shown in Figure 4 , 5 . It can be seen from Figure 4 , 5 that in the infrared spectrum of the 50FPAE sample, the absorption peaks at 3388 cm -1 , 3490 cm -1 are attributed to the stretching vibration of N-H, and 1626 cm-1 The bending vibration peak attributed to N-H. After introducing bismaleimide, in the infrared spectrum of the 50FPAE-PI sample, the characteristic peak of N-H disappeared. Meanwhile, at 661 cm -1 the stretching vibration peak of the carbon-carbon double bond (C=C) on the maleimide ring was observed. At 3083 cm -1 the out-of-plane vibration peak of =C-H was observed. At 1776 cm -1 and 1703 cm -1 the asymmetric stretching vibration and symmetric stretching vibration peaks of the C=O bond appeared. After high-temperature curing and crosslinking, in the infrared spectrum of the CL-50FPAE-PI sample, the related characteristic peaks of C=C disappeared.

[0102] The fluorinated polyarylether film containing amino structure was prepared according to the following method:

[0103] The fluorinated polyarylether containing amino structure obtained in step (1) of Example 2 (2 g) was dissolved in N-methyl-2-pyrrolidone (20 mL) at 50 °C, filtered through a sintered glass funnel, and then cast on a glass mold. The solvent was dried in an oven, and the drying procedure was to dry at 80 °C, 100 °C, 120 °C, 140 °C, 160 °C, 180 °C, and 200 °C for 2 h in sequence; after naturally cooling to 30 °C, the film was peeled off to obtain the fluorinated polyarylether film containing amino structure (denoted as 50FPAE) for thermal property and dielectric property tests.

[0104] The fluorinated polyarylether containing bismaleimide obtained in step (2) of Example 2 (2 g) was dissolved in N-methyl-2-pyrrolidone (20 mL) at 55 °C, filtered through a sintered glass funnel, and then cast on a glass mold. The solvent was dried in an oven, and the drying procedure was to dry at 80 °C, 100 °C, 120 °C, 140 °C, 160 °C, 180 °C, and 200 °C for 2 h in sequence; the dried film was thermally cured at 280 °C for 2 h to obtain the crosslinked polyarylether film material containing bismaleimide structure (denoted as CL-50FPAE-PI) for thermal property and dielectric property tests. Different tests have different requirements for the film thickness. For infrared characterization, a film with a small thickness is required. If the film is too thick, the transmittance will decrease, the error will increase, and a spectrum with absorption peaks cannot be obtained. For thermal property and dielectric property tests, a film with a larger thickness is required. If the film is too thin, the electric field cannot be evenly distributed in the sample, a stable electric field cannot be formed, resulting in inaccurate test results; therefore, a crosslinked polyarylether film material with a larger thickness containing bismaleimide structure was prepared here for thermal property and dielectric property tests.

[0105] The prepared 50FPAE and the crosslinked polyarylether membrane material containing bismaleimide structure were tested with a TH2826 type LCR digital bridge at room temperature (25 °C). The test frequency range was 10 Hz to 10 6 Hz, and the relationship diagrams of the dielectric constant and dielectric loss with the change of electric field frequency are as shown in Figure 6 Figure. It can be seen from Figure 6 Figure that the dielectric constants of both the 50FPAE and CL-50FPAE-PI samples decrease with the increase of frequency. The dielectric constant of the 50FPAE sample is in the range of 2.96 - 3.38, and the dielectric constant of the CL-50FPAE-PI sample is in the range of 2.12 - 2.51. The dielectric constant of the CL-50FPAE-PI sample is lower than that of 50FPAE, which benefits from the disappearance of polar amino groups and the formation of a crosslinked network.

[0106] The prepared 50FPAE and CL-50FPAE-PI prepared in Example 2 were subjected to thermogravimetric analysis using a TG 209F3 thermogravimetric analyzer. The test conditions were in a nitrogen environment, with a heating rate of 20 °C / min from 50 °C to 800 °C. The glass transition temperatures of 50FPAE and CL-50FPAE-PI prepared in Example 2 were tested using a Pyris 1 differential scanning calorimeter produced by Perkin Elmer. The test conditions were in a nitrogen environment, with a heating rate of 10 °C / min from 50 °C to 300 °C. The test results are listed in Table 1.

[0107] Table 1 Thermal properties of 50FPAE and CL-50FPAE-PI prepared in Example 2

[0108] sample <![CDATA[T 5％ (℃)]]> <![CDATA[T max (℃)]]> <![CDATA[T g (℃)]]> 50FPAE 379 564 188 CL-50FPAE-PI 445 563 221

[0109] In Table 1, T 5％ is the temperature at 5% weight loss; T max is the temperature at the maximum decomposition rate; T g is the glass transition temperature.

[0110] It can be seen from Table 1 that the T 5％ and T g of CL-50FPAE-PI are both higher than those of 50FPAE, and T g is even as high as 221 °C. After high-temperature thermal crosslinking, a three-dimensional network structure is formed inside the polymer, improving the heat resistance and increasing T 5％ ; the formation of the crosslinked network increases the degree of hindrance to the movement of chain segments and increases T g . CL-50FPAE-PI has better thermal properties, which all benefit from the formation of the crosslinked network.

[0111] The 50FPAE and CL-50FPAE-PI prepared in Example 2 were tested in accordance with GB / T 10801-2006 "Tensile Test of Plastic Films and Sheets", and the mechanical properties are listed in Table 2.

[0112] Table 2 Mechanical properties of 50FPAE and CL-50FPAE-PI prepared in Example 2

[0113]

[0114] It can be seen from Table 2 that both the tensile strength and tensile modulus of CL-50FPAE-PI are higher than those of 50FPAE. The formed crosslinked network hinders the movement of polymer chains, increasing the rigidity of the polymer and the tensile strength of CL-50FPAE-PI. When stretching, the external force needs to overcome the restraint between crosslinking points, increasing the modulus of CL-50FPAE-PI.

[0115] The properties of the crosslinked polyarylether membrane materials containing bismaleimide structure prepared in Example 1 and Example 3 are similar to those of the crosslinked polyarylether membrane materials containing bismaleimide structure prepared in Example 2.

[0116] Although the above embodiments have described the present invention in detail, they are only a part of the embodiments of the present invention, not all of them. People can also obtain other embodiments based on these embodiments without creative efforts, and these embodiments all fall within the protection scope of the present invention.

Claims

1. A cross-linked polyarylether film material containing a bismaleimide structure, characterized in that: It has the structure shown in formula 1: Wherein, x is any value between 0.4 and 0.6, and n is any integer between 60 and 80.

2. The method for preparing the cross-linked polyarylether membrane material containing bismaleimide structure according to claim 1, characterized in that: The following steps are involved: 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane, 2,2-bis(4-hydroxyphenyl)hexafluoropropane, perfluorobiphenyl, anhydrous potassium carbonate and N,N-dimethylacetamide are first mixed and then subjected to an aromatic nucleophilic substitution reaction to obtain compound 1; The compound 1, maleic anhydride and N-methyl-2-pyrrolidone are mixed for a second time, and then mixed with a catalyst and a dehydrating agent for a third time to perform a dehydration cyclization reaction to obtain a compound 2; The compound 2 is dissolved in N-methyl-2-pyrrolidone and then molded and thermally cured in sequence to obtain the cross-linked polyarylether film material containing a bismaleimide structure; The compound 1 has a structure shown in Formula 2, and the compound 2 has a structure shown in Formula 3:

3. The preparation method according to claim 2, characterized in that: The molar ratio of 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane to 2,2-bis(4-hydroxyphenyl)hexafluoropropane is 4:6 to 6:4; The molar ratio of the total molar amount of the 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane and 2,2-bis(4-hydroxyphenyl)hexafluoropropane to perfluorobiphenyl is 1:1; The molar ratio of anhydrous potassium carbonate to perfluorobiphenyl is 1 to 2:1; The mass ratio of the total mass of the 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane, 2,2-bis(4-hydroxyphenyl)hexafluoropropane and perfluorobiphenyl to the mass ratio of N,N-dimethylacetamide is 1:3.5-6.

4. The preparation method according to claim 2 or 3, characterized in that: The temperature of the aromatic nucleophilic substitution reaction is 80-90° C. and the time is 4-5 hours.

5. The preparation method according to claim 2, characterized in that: The compound 1 includes an amino-containing structural unit, and the amino-containing structural unit is The molar amount of maleic anhydride is 2 to 2.1 times the molar number of amino-containing structural units in compound 1; The mass ratio of the total mass of the compound 1 and maleic anhydride to N-methyl-2-pyrrolidone is 0.05-0.15:1; The catalyst includes triethylamine, and the molar amount of the catalyst is 3 to 4 times the molar number of the amino-containing structural unit in compound 1; The dehydrating agent includes acetic anhydride, and the molar amount of the dehydrating agent is 3 to 4 times the molar number of the amino-containing structural unit in compound 1.

6. The preparation method according to claim 2 or 5, characterized in that: The temperature of the dehydration cyclization reaction is 90-100° C. and the time is 6-8 hours.

7. The preparation method according to claim 2, characterized in that: The molding is performed by dissolving compound 2 in N-methyl-2-pyrrolidone and filtering the solution, casting the filtered solution in a mold and drying the solution.

8. The preparation method according to claim 7, characterized in that: The mass ratio of the molding N-methyl-2-pyrrolidone to the compound 2 is 8.5 to 15:1; The drying procedure is to keep the temperature at 80°C, 100°C, 120°C, 140°C, 160°C, 180°C and 200°C for 2 hours respectively.

9. The preparation method according to claim 2, 7 or 8, characterized in that: The thermal curing temperature is 270-280° C. and the time is 2-4 hours.

10. Use of the cross-linked polyarylether film material containing bismaleimide structure according to claim 1 or the cross-linked polyarylether film material containing bismaleimide structure prepared by the preparation method according to any one of claims 2 to 9 as a low dielectric material in microelectronics.

Images