Hyperbranched boric acid-modified phthalonitrile monomer, its production method and application

Abstract

This application discloses a hyperbranched boric acid modified phthalonitrile monomer and its preparation method and application. The preparation method of the hyperbranched boric acid modified phthalonitrile monomer includes reacting a first mixed reaction system containing a boron source, a phenolic compound, and a solvent to obtain a compound containing a BO structure, and reacting a second mixed reaction system containing the compound containing a BO structure, 4-nitrophthalonitrile, a catalyst, and a solvent to obtain a hyperbranched boric acid modified phthalonitrile monomer. The hyperbranched boric acid modified phthalonitrile monomer prepared in this application can be dissolved in various organic solvents, and the processing performance of the phthalonitrile monomer is improved, and the modified phthalonitrile resin prepared from the phthalonitrile monomer has excellent high temperature resistance and seizure resistance, which has a wide application prospect in the fields of aerospace, warships, submarines, electronic packaging and the like.

Description

Technical Field

[0001] [Cross - reference to Related Applications] This application is based on and claims priority to a Chinese patent application with an application number of 202111329850.2, filed on November 10, 2021, and titled "Hyperbranched Boric Acid - Modified Phthalonitrile Monomer and Its Manufacturing Method and Application". This application belongs to the field of composite material technology, and specifically relates to hyperbranched boric acid - modified phthalonitrile monomers and their manufacturing methods and applications.

Background Art

[0002] Phthalonitrile resin, also known as o - phthalonitrile resin, is a high - temperature - resistant resin developed by Keller and his team at the US Naval Laboratory in the 1980s. As shown in Figure 1, it is a thermosetting resin obtained by addition cross - linking of cyano groups to monomers having an o - phthalonitrile structure. Compared with some other common high - temperature - resistant resins, phthalonitrile resin shows excellent high - temperature stability after appropriate post - curing treatment. Under the conditions of air and nitrogen gas, the decomposition temperature T 5% is above 500 °C. At 400 °C, no glass transition temperature or softening phenomenon is observed, and the long - term use temperature is as high as 372 °C. Due to the addition - curing mechanism, there is no generation of small - molecule by - products during its curing stage, the resulting resin structure is dense, and it has excellent dimensional stability. The polymer has good mechanical properties, excellent high - temperature resistance performance and low water absorption rate, and further has the characteristics of being flame - retardant, low - toxicity, and smokeless. It is the only special fire - resistant polymer material that meets the US military standard (MIL - STD - 2031)) and can be used in fields such as aerospace, ships, micro - electronics, and mechanical manufacturing.

Summary of the Invention

Problems to be Solved by the Invention

[0003] The main object of this application is to provide a hyperbranched boric acid modified phthalonitrile monomer, its manufacturing method and applications to overcome the drawbacks of the prior art.

Means for Solving the Problems

[0004] To achieve the object of the invention described above, the technical solution used in this application includes the following. Examples of this application provide a hyperbranched boric acid modified phthalonitrile monomer, and the phthalonitrile monomer has a structure shown in formula (I), JPEG0007696062000001.jpg4780 Here, R, R', and R'' are all independently selected from aromatic structures. Examples of this application further provide a method for manufacturing the hyperbranched boric acid modified phthalonitrile monomer described above, and this method includes reacting a first mixed reaction system containing a boron source, a phenolic compound, and a solvent to obtain a compound containing a B-O structure, and reacting a second mixed reaction system containing the compound containing the B-O structure, 4-nitrophthalonitrile, a catalyst, and a solvent to obtain the hyperbranched boric acid modified phthalonitrile monomer. Examples of this application further provide a method for manufacturing a modified phthalonitrile resin, and this method includes providing the hyperbranched boric acid modified phthalonitrile monomer described above, and subjecting the phthalonitrile monomer and a phthalonitrile curing agent to a curing reaction to obtain a modified phthalonitrile resin. Examples of this application further provide a modified phthalonitrile resin manufactured by the method described above. Examples of this application further provide the applications of the hyperbranched boric acid modified phthalonitrile monomer described above or the modified phthalonitrile resin described above in the fields of aerospace, ships, microelectronics or mechanical manufacturing.

Advantages of the Invention

[0005] Compared with the prior art, the beneficial effects of this application are as follows. (1) This application first introduces a hyperbranched B-O structure into the o-phthalonitrile monomer, and has a simple synthesis method and versatility. (2) The hyperbranched boric acid-modified phthalonitrile monomer produced in this application is soluble in common organic solvents, improving the processability of the phthalonitrile monomer. (3) This application introduces the structure of hyperbranched boric acid or hyperbranched boric acid derivatives into the o-phthalonitrile monomer, and the introduction of boron improves the baking resistance and high-temperature resistance of the resin.

Brief Description of the Drawings

[0006]

Figure 1

Figure 2

Figure 3

Figure 4

Modes for Carrying Out the Invention

[0007] To more clearly explain the technical solutions in the examples or the prior art of this application, the following briefly introduces the attached drawings that need to be used in the description of the examples or the prior art. Obviously, the attached drawings in the following description are only some examples described in this application. On the premise that no creative effort is required for those skilled in the art, other attached drawings can also be obtained based on these attached drawings.

[0008] In view of the deficiencies of the prior art, the inventors of the present application have, through long-term research and a large amount of practice, proposed the technical solution of the present application. The following clearly and completely describes the technical solution of the present application. Obviously, the described embodiments are some embodiments of the present application, not all embodiments. Based on the embodiments in the present application, all other embodiments obtained without creative efforts by those skilled in the art all belong to the protection scope of the present application.

[0009] Specifically, as an aspect of the technical solution of the present application, the hyperbranched boric acid-modified phthalonitrile monomer thereof has a structure shown in formula (I), JPEG0007696062000002.jpg4680Here, R, R', and R'' are all independently selected from aromatic structures.

[0010] Furthermore, the aromatic structure includes, but is not limited to, benzene rings and / or aromatic ethers.

[0011] In some preferred embodiments, the phthalonitrile monomer has a structure shown in formula (II). JPEG0007696062000003.jpg76113Furthermore, the molecular structure of the phthalonitrile monomer contains a hyperbranched boric acid structure or a structure of a hyperbranched boric acid derivative.

[0012] According to another aspect of the embodiments of the present application, a method for producing the aforementioned hyperbranched boric acid-modified phthalonitrile monomer is further provided, and this method includes reacting a first mixed reaction system containing a boron source, a phenolic compound, and a solvent to obtain a compound containing a B-O structure, reacting a second mixed reaction system containing the compound containing the B-O structure, 4-nitrophthalonitrile, a catalyst, and a solvent to obtain the hyperbranched boric acid-modified phthalonitrile monomer.

[0013] In some preferred embodiments, the manufacturing method specifically includes mixing a phenolic compound and a first solvent, adding a boron source under a shielding gas atmosphere to form the first mixed reaction system, reacting at 100 to 160 °C for 3 h to obtain the compound containing the B-O structure.

[0014] In some preferred embodiments, the manufacturing method specifically includes mixing the compound containing the B-O structure and a solvent, further adding 4-nitrophthalonitrile and a catalyst to form the second mixed reaction system, and reacting at 30 to 80 °C for 12 to 18 h under a shielding gas atmosphere to obtain the hyperbranched boric acid modified phthalonitrile monomer.

[0015] In some preferred embodiments, the boron source includes, but is not limited to, boric acid and / or phenylboronic acid.

[0016] Furthermore, the phenolic compound includes, but is not limited to, any one or a combination of two or more of resorcinol, phloroglucinol, bisphenol-A, bisphenol-F, or 1,3,5-benzenetriol.

[0017] Furthermore, the catalyst includes, but is not limited to, a basic catalyst.

[0018] Even further, the basic catalyst includes, but is not limited to, potassium carbonate.

[0019] Furthermore, the solvent includes, but is not limited to, N-methylpyrrolidone.

[0020] In some preferred embodiments, the molar ratio of the boron source to the phenolic compound is 10:1 to 1:10.

[0021] Furthermore, the molar ratio of the compound containing the B-O structure, 4-nitrophthalonitrile, and the catalyst is 1:1 to 4:1 to 4.

[0022] According to another aspect of the embodiments of the present application, a method for manufacturing a modified phthalonitrile resin is further provided, and this method includes: providing the above-mentioned hyperbranched boric acid modified phthalonitrile monomer; performing a curing reaction on the phthalonitrile monomer and a phthalonitrile curing agent to obtain a modified phthalonitrile resin.

[0023] In some preferred embodiments, the phthalonitrile curing agent includes, but is not limited to, any one or a combination of two or more of an organic amine-based curing agent, a phenolic curing agent, a strong organic acid-based curing agent, a strong organic acid / ammonium salt curing agent, a metal salt-based curing agent, and a metal curing agent.

[0024] Furthermore, the organic amine-based curing agent includes, but is not limited to, any one or a combination of two or more of 4,4'-(1,4-benzenedioxy)bisaniline curing agent, 4,4'-bis(4-aminophenoxy)diphenyl sulfone, 4,4'-bis(3-aminophenoxy)diphenyl sulfone, and 4,4'-diaminodiphenyl sulfone.

[0025] In some preferred embodiments, the manufacturing method specifically includes mixing the phthalonitrile monomer and the phthalonitrile curing agent and performing a curing reaction at 150 - 600°C.

[0026] In some more specific embodiments, the compound containing the B-O structure is obtained by the reaction of boric acid and a phenolic compound.

[0027] Furthermore, boric acid and resorcinol are charged in a molar ratio of 10:1 to 1:10, N-methylpyrrolidone (NMP) is selected as the solvent, and the reaction is carried out at 100 - 160°C for 3 h under an inert gas atmosphere to obtain a compound containing the B-O structure.

[0028] In some more specific embodiments, the hyperbranched boric acid modified phthalonitrile monomer is obtained by reacting the compound containing the B-O structure with 4-nitrophthalonitrile, and the boron source is introduced into the o-phthalonitrile monomer.

[0029] Furthermore, using potassium carbonate as a basic catalyst, N-methylpyrrolidone or the like as a solvent, the compound containing the B-O structure (the compound containing the B-O structure contains an -OH structure) and 4-nitrophthalonitrile as raw materials, reacting at 30-80 °C for 12-18 h under an inert gas atmosphere to obtain an o-phthalonitrile monomer containing a hyperbranched B-O structure (that is, the aforementioned "hyperbranched boric acid modified phthalonitrile monomer").

[0030] In some more specific embodiments, the modified phthalonitrile resin is obtained by mixing an o-phthalonitrile monomer containing a hyperbranched B-O structure and a phthalonitrile curing agent and curing under certain conditions.

[0031] Furthermore, the curing condition of the phthalonitrile resin is to increase the temperature gradually from 150 °C to 600 °C.

[0032] According to another aspect of the embodiments of the present application, a modified phthalonitrile resin manufactured by the aforementioned method is further provided.

[0033] In the present application, the phthalonitrile monomer is soluble in common organic solvents such as tetrahydrofuran, N,N-dimethylformamide, dimethyl sulfoxide, acetone, dichloromethane, N-methylpyrrolidone solvent, etc., has good processability, and the resin obtained by manufacturing, when not post-cured at high temperature, has a thermal stability T 5% = 411 °C, and the char residue rate at 1000 °C is 45.68%. The thermal oxidation stability T 5% = 411 °C, has good heat resistance, the heat release peak value of the resin is low, the total heat release is small, indicating that the modified phthalonitrile resin has good anti-fouling properties.

[0034] In this application, boron in the modified phthalonitrile resin forms a heat-insulating protective layer on the surface of the carbide during the thermal decomposition process. The electron deficiency of boron atoms attracts electrons from adjacent carbon atoms during the thermal decomposition process, thereby breaking the covalent bond between the carbon atoms and the rearranged carbon skeleton structure. As a result, the thermal decomposition rate of the resin decreases as amorphous carbon changes to a more regular graphite carbon structure.

[0035] According to another aspect of the embodiments of this application, the use of the aforementioned hyperbranched boric acid modified phthalonitrile monomer or the aforementioned modified phthalonitrile resin in the fields of aerospace, ships, microelectronics or mechanical manufacturing is further provided.

[0036] Hereinafter, with reference to a plurality of preferred embodiments and the accompanying drawings, the technical solutions of this application will be described in more detail. This embodiment is implemented on the premise of the technical solutions of the invention, showing detailed embodiments and specific operation processes, but the protection scope of this application is not limited to the following embodiments.

[0037] The experimental materials used in the following examples can be purchased from ordinary biochemical reagent companies unless otherwise specified.

[0038] Example 1 In this example, phthalonitrile monomer was produced using boric acid, resorcinol and 4-nitrophthalonitrile monomer as raw materials. All of these raw materials can be obtained by methods such as commercial purchase. The production method is as follows.

[0039] (1) 150 mL of NMP was added to 33.033 g of resorcinol (0.3 mol), and it was stirred and dissolved at 60 °C.

[0040] (2) N2 was injected for purging.

[0041] (3) 6.183 g of boric acid (0.1 mol) was added, and the reaction was carried out at 100 °C for 3 h under an N2 atmosphere.

[0042] (4) Subsequently, 55.28 g of K2CO3 (0.4 mol) and 17.313 g of 4-nitrophthalonitrile (0.1 mol) were added to the system, and the reaction was carried out at 30 °C for 18 h under a N2 atmosphere.

[0043] (5) The impurities in the system were removed by washing with water.

[0044] (6) The product was placed in an oven and dried at 80 °C for 12 h to obtain a powdery sample of the hyperbranched boric acid-modified phthalonitrile monomer.

[0045] Example 2 In this example, phthalonitrile monomer was produced using boric acid, resorcinol, and 4-nitrophthalonitrile monomer as raw materials. All of these raw materials can be obtained by methods such as commercial purchase. The production method is as follows.

[0046] (1) 150 mL of NMP was added to 33.033 g of resorcinol (0.3 mol), and the mixture was stirred and dissolved at 60 °C.

[0047] (2) N2 was introduced and purging was carried out.

[0048] (3) 6.183 g of boric acid (0.1 mol) was added, and the reaction was carried out at 130 °C for 3 h under a N2 atmosphere.

[0049] (4) Subsequently, 49.754 g of K2CO3 (0.36 mol) and 69.252 g of 4-nitrophthalonitrile (0.4 mol) were added to the system, and the reaction was carried out at 50 °C for 15 h under a N2 atmosphere.

[0050] (5) The impurities in the system were removed by washing with water.

[0051] (6) The product was placed in an oven and dried at 80 °C for 12 h to obtain a powdery sample of the hyperbranched boric acid-modified phthalonitrile monomer.

[0052] Example 3 In this example, phthalonitrile monomer was produced using boric acid, resorcinol, and 4-nitrophthalonitrile monomer as raw materials. All of these raw materials can be obtained by methods such as commercial purchase. The production method is as follows.

[0053] (1) 150 mL of NMP was added to 33.033 g of resorcinol (0.3 mol), and the mixture was stirred and dissolved at 60 °C.

[0054] (2) N2 was injected and purging was performed.

[0055] (3) 6.183 g of boric acid (0.1 mol) was added, and the reaction was carried out at 160 °C for 3 h under a N2 atmosphere to obtain tris-(3-hydroxyphenyl) borate ester. The reaction formula is as shown in the following formula. JPEG0007696062000004.jpg41112

[0056] (4) Subsequently, 49.754 g of K2CO3 (0.36 mol) and 51.939 g of 4-nitrophthalonitrile (0.3 mol) were added to the system, and the reaction was carried out at 80 °C for 12 h under a N2 atmosphere.

[0057] (5) The impurities in the system were removed by washing with water.

[0058] (6) The product was placed in an oven and dried at 80 °C for 12 h to obtain a dark green powder, which is a hyperbranched boric acid modified phthalonitrile monomer (the solubility of the monomer is as shown in Table 1). The reaction formula is as shown in the following formula. JPEG0007696062000005.jpg65148 Example 4 In this example, phthalonitrile monomer was produced using phenylboronic acid, resorcinol, and 4-nitrophthalonitrile monomer as raw materials. All of these raw materials can be obtained by methods such as commercial purchase. The production method is as follows.

[0059] (1) 150 mL of NMP was added to 22.022 g of resorcinol (0.2 mol), and the mixture was stirred and dissolved at 60 °C.

[0060] (2) N2 was poured in and purging was carried out.

[0061] (3) 12.193 g of phenylboronic acid (0.1 mol) was added, and the reaction was carried out at 120 °C for 3 h under a N2 atmosphere to obtain bis-(3-hydroxyphenyl)phenyl boronic acid ester. JPEG0007696062000006.jpg20119(4) Subsequently, 49.754 g of K2CO3 (0.36 mol) and 34.626 g of 4-nitrophthalonitrile (0.2 mol) were added to the system, and the reaction was carried out at 50 °C for 15 h under a N2 atmosphere. JPEG0007696062000007.jpg21164

[0062] (5) Impurities in the system were removed by washing with water.

[0063] (6) The product was placed in an oven and dried at 80 °C for 12 h to obtain a powdery sample of hyperbranched boric acid modified phthalonitrile monomer.

[0064] Performance expression: JPEG0007696062000008.jpg52144

[0065] Example 5 In this example, phthalonitrile monomer was produced using phenylboronic acid, resorcinol and 4-nitrophthalonitrile monomer as raw materials. All of these raw materials can be obtained by methods such as commercial purchase. The production method is as follows.

[0066] (1) 150 mL of NMP was added to 22.022 g of resorcinol (0.2 mol), and the mixture was stirred and dissolved at 60 °C.

[0067] (2) N2 was poured in and purging was carried out.

[0068] (3) 12.193 g of phenylboronic acid (0.1 mol) was added, and the reaction was carried out at 120 °C for 3 h under a N2 atmosphere.

[0069] (4) Subsequently, 13.821 g of K2CO3 (0.1 mol) and 34.626 g of 4-nitrophthalonitrile (0.2 mol) were added to the system, and the reaction was carried out at 50 °C for 15 h under a N2 atmosphere.

[0070] (5) Impurities in the system were removed by washing with water.

[0071] (6) The product was placed in an oven and dried at 80 °C for 12 h to obtain a powdery sample of the hyperbranched boric acid-modified phthalonitrile monomer.

[0072] Performance representation: Figure 1 is a schematic diagram of obtaining a thermosetting resin by performing addition crosslinking of a cyano group to a monomer having an o-phthalonitrile structure in the prior art of this application.

[0073] Figure 2 is a representation of the FTIR structure of the hyperbranched boric acid-modified phthalonitrile monomer produced in Example 3, and the peak of the newly generated aromatic ether bond at 1250 cm -1 appeared, indicating that the production of the phthalonitrile monomer containing a hyperbranched boric acid structure was successful.

[0074] Figure 3 is the TGA result of the modified phthalonitrile resin produced in Example 5. For this resin, in an air atmosphere, T 5% = 413 °C, and in an argon gas atmosphere, T 5% = 411 °C, indicating that such a novel modified phthalonitrile resin has good thermal stability.

[0075] Figure 4 is the PCFC curve of the modified phthalonitrile resin produced in Example 5. The results show that the heat release peak value of the resin is low, the total heat release is small, indicating that the modified phthalonitrile resin has good anti-burnability.

[0076] Example 6 In this example, phthalonitrile monomer was produced using phenylboronic acid, bisphenol A, and 4-nitrophthalonitrile monomer as raw materials. All of these raw materials can be obtained by methods such as commercial purchase. The production method is as follows.

[0077] (1) 150 mL of NMP was added to 68.4 g of bisphenol A (0.3 mol), and the mixture was stirred and dissolved at 60 °C.

[0078] (2) N2 was injected and purging was carried out.

[0079] (3) 12.193 g of phenylboronic acid (0.1 mol) was added, and the reaction was carried out at 120 °C for 3 h under a N2 atmosphere.

[0080] (4) Subsequently, 49.754 g of K2CO3 (0.36 mol) and 34.626 g of 4-nitrophthalonitrile (0.4 mol) were added to the system, and the reaction was carried out at 50 °C for 15 h under a N2 atmosphere.

[0081] (5) Impurities in the system were removed by washing with water.

[0082] (6) The product was placed in an oven and dried at 80 °C for 12 h to obtain a powdery sample of hyperbranched boric acid-modified phthalonitrile monomer.

[0083] Example 7 The hyperbranched boric acid-modified phthalonitrile monomer in this example was obtained according to Example 3, and it was mixed with a curing agent to produce a modified phthalonitrile resin. The specific method is as follows.

[0084] 4 g of hyperbranched boric acid-modified phthalonitrile monomer and 0.4 g of 4,4'-bis(4-aminophenoxy) diphenyl sulfone curing agent were dissolved in 15 mL of acetone, mixed uniformly, and the excess solvent was removed. Then the mixture was placed in a mold and put into a vacuum oven to remove the remaining solvent.

[0085] The hybrid system was subjected to a curing process at 150 °C for 2 h, 180 °C for 2 h, 220 °C for 2 h, 260 °C for 2 h, and 280 °C for 2 h to obtain a modified phthalonitrile resin.

[0086] Example 8 The hyperbranched boric acid modified phthalonitrile monomer in this example was obtained according to Example 3, and it was mixed with a curing agent to produce a modified phthalonitrile resin. The specific method is as follows.

[0087] 4 g of the hyperbranched boric acid modified phthalonitrile monomer and 0.4 g of the 4,4'-(1,4-benzenedioxy)bisaniline curing agent were dissolved in 15 mL of acetone, mixed uniformly, and the excess solvent was removed. Then the mixture was placed in a mold and put into a vacuum oven to remove the remaining solvent.

[0088] The hybrid system was subjected to a curing process at 150 °C for 2 h, 180 °C for 2 h, 220 °C for 2 h, 260 °C for 2 h, and 280 °C for 2 h to obtain a modified phthalonitrile resin.

[0089] In short, compared with the conventional o-phthalonitrile monomer, the novel monomer produced in this application has good solubility. The obtained modified phthalonitrile resin has the advantages of being resistant to high temperatures and baking.

[0090] It should be noted that the inventors of this application have also conducted tests under other raw materials, process operations, and process conditions mentioned in this specification while further referring to the foregoing examples, and all have obtained ideal results.

[0091] It should be understood that the technical solution of this application is not limited to the above specific implementation cases. As long as it does not deviate from the spirit of this application and the scope protected by the claims, any technical deformation based on the technical solution of this application falls within the protection scope of this application.

Claims

1. A hyperbranched boric acid modified phthalonitrile monomer, wherein the phthalonitrile monomer has a structure represented by formula (I), A hyperbranched boric acid modified phthalonitrile monomer, characterized by the above.

2. The phthalonitrile monomer is characterized by having a structure represented by formula (II) The hyperbranched boric acid modified phthalonitrile monomer according to claim 1.

3. A method for producing the hyperbranched boric acid modified phthalonitrile monomer according to claim 1 or claim 2, comprising: Reacting a first mixed reaction system containing a boron source, a phenolic compound, and a solvent to obtain a compound containing a B-O structure; Reacting a second mixed reaction system containing the compound containing a B-O structure, 4-nitrophthalonitrile, a catalyst, and a solvent to obtain the hyperbranched boric acid modified phthalonitrile monomer, The boron source includes boric acid and / or phenylboronic acid, The phenolic compound includes resorcinol. A production method characterized by the above.

4. Specifically including mixing a phenolic compound and a first solvent, adding a boron source under a shield gas atmosphere to form the first mixed reaction system, and reacting at 100-160°C for 3 h to obtain the compound containing a B-O structure. The production method according to claim 3.

5. Specifically including mixing the compound containing a B-O structure and a solvent, further adding 4-nitrophthalonitrile and a catalyst to form the second mixed reaction system, and reacting at 30-80°C for 12-18 h under a shield gas atmosphere to obtain the hyperbranched boric acid modified phthalonitrile monomer. The production method according to claim 3.

6. The catalyst contains a basic catalyst, preferably, the basic catalyst contains potassium carbonate, and / or the solvent contains N-methylpyrrolidone, characterized in that The production method according to claim 3.

7. The molar ratio of the boron source to the phenolic compound is 10:1 to 1:10, and / or the molar ratio of the compound containing the B-O structure, 4-nitrophthalonitrile, and the catalyst is 1:1 to 4:1 to 4, characterized in that The production method according to claim 3.

8. A method for producing a modified phthalonitrile resin, comprising: providing the hyperbranched boric acid modified phthalonitrile monomer according to claim 1 or claim 2; subjecting the phthalonitrile monomer and a phthalonitrile curing agent to a curing reaction to obtain a modified phthalonitrile resin. A method for producing a modified phthalonitrile resin, characterized by including this.

9. The phthalonitrile curing agent contains any one or a combination of two or more of an organic amine curing agent, a phenolic curing agent, a strong organic acid curing agent, a strong organic acid / ammonium salt curing agent, a metal salt curing agent, and a metal curing agent, characterized in that The production method according to claim 8.

10. The organic amine curing agent contains any one or a combination of two or more of 4,4'-(1,4-benzenedioxy)bisaniline curing agent, 4,4'-bis(4-aminophenoxy)diphenyl sulfone, 4,4'-bis(3-aminophenoxy)diphenyl sulfone, and 4,4'-diaminodiphenyl sulfone, characterized in that The production method according to claim 9.

11. The mass ratio of the phthalonitrile monomer to the phthalonitrile curing agent is 100:(1 to 30), characterized in that The production method according to claim 8. Claim 12 Specifically including mixing the phthalonitrile monomer and the phthalonitrile curing agent and carrying out a curing reaction at 150 to 600 °C, characterized by The production method according to claim 8. Claim 13 The hyperbranched boric acid modified phthalonitrile monomer according to claim 1 or claim 2, which is a hyperbranched boric acid modified phthalonitrile monomer for aerospace, ship, microelectronics or machinery manufacturing.

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