Preparation method of high-temperature-resistant antioxidant phthalonitrile cyano resin

Abstract

The invention relates to the technical field of phthalonitrile resin, and discloses a preparation method of high-temperature-resistant and antioxidant phthalonitrile cyano resin, which is characterized in that biphenyl bisphthalonitrile and phthalonitrile fluorine-containing polyetherimide are subjected to thermocuring to obtain the high-temperature-resistant and antioxidant phthalonitrile cyano resin. The phthalonitrile fluorine-containing polyetherimide contains a heat-resistant triazine ring and an imide ring, and is subjected to co-curing cross-linking reaction into a phthalonitrile resin molecular chain, so that the high-temperature mass loss temperature of the resin is increased, the resin shows better high-temperature resistance, after high-temperature hot air aging, the bending strength is small in reduction amplitude, the retention rate is high, and the service life of the resin is prolonged. Better high temperature resistance and oxidation resistance are shown. The phthalonitrile fluorine-containing polyetherimide contains a hydrophobic trifluoromethyl group which is crosslinked into a phthalonitrile resin molecular chain to form a hydrophobic crosslinked network, so that the hydrophobicity of the resin is facilitated, and the water absorption rate is reduced.

Description

Technical Field

[0001] The invention relates to the technical field of phthalonitrile resins, in particular to a method for preparing a high-temperature-resistant and anti-oxidative phthalonitrile cyano resin. Background Art

[0002] Nitrile-based resins mainly include phthalonitrile resins, biphenyl-type diphthalonitrile resins, bisphenol A-type phthalonitrile resins, benzoxazine phthalonitrile resins, etc. They are high-performance thermosetting resins. At high temperatures, cyano groups can undergo addition polymerization reactions to generate structures such as phthalocyanine rings, showing excellent properties such as high temperature resistance and mechanical strength, and are resistant to long-term thermal oxidation at 450°C-500°C. Through molecular structure and formula design, a phthalonitrile resin system with high load-bearing capacity and low thermal decomposition at high temperatures is obtained. It is matched with carbon fiber, glass fiber and other materials to form a structural composite material, which can meet the mechanical properties, heat resistance and process properties required by high-pressure and high-temperature resistant structural materials for supersonic aircraft and submarines, and the material cost and process cost are moderate. It is widely used in aerospace, automotive industry, electronic and electrical fields. However, traditional phthalonitrile resins such as biphenyl-type diphthalonitrile have problems such as greater brittleness, poor toughness, and poor bending performance, which limit its development and application.

[0003] At present, polyarylether nitrile, polyether sulfone, polyether imide, etc. are mainly used to toughen and modify phthalonitrile resin. The patent application document with publication number CN114773844A discloses a polyimide toughened phthalonitrile resin composition, a composite material and a preparation method thereof. The phthalonitrile resin is toughened by a polyimide resin containing a cyano functional group, which solves the problem of poor compatibility between thermoplastic resin and phthalonitrile resin and improves the mechanical properties of phthalonitrile resin. Compared with the patent authorization, the present invention not only improves the toughness and mechanical strength of phthalonitrile resin, but also improves the high temperature resistance, oxidation resistance and other properties of phthalonitrile resin. Summary of the invention

[0004] (I) Technical problems to be solved: In view of the deficiencies in the prior art, the present invention provides a method for preparing a phthalonitrile cyano resin having good toughness, high temperature resistance and oxidation resistance.

[0005] (II) In order to solve the above technical problems, the present invention adopts the following technical scheme: A method for preparing a high temperature resistant and antioxidant phthalonitrile cyano resin:

[0006] (1) Nitrogen is introduced into a reaction vessel, and N-methylpyrrolidone, 4,4-biphenyl ether dianhydride, fluorine-containing aminotriazine monomer, and 2,2-bis(3-amino-4-hydroxyphenyl)propane (CAS No. 1220-78-6) are added, and the mixture is reacted at room temperature for 18-24 hours. After the reaction, the solution is poured onto a glass plate, and heat cured at 100-300°C for 5-7 hours, and the film is removed to obtain a hydroxyl fluorine-containing polyetherimide. The reaction formula is as follows:

[0007]

[0008] (2) Add N,N-dimethylformamide and hydroxy fluorinated polyetherimide to a reaction vessel, stir and dissolve, then add potassium carbonate and 4-nitrophthalonitrile, react at 80-90°C for 6-12h, cool and add water to the solution to precipitate, filter and wash with water and ethanol, and dry to obtain fluorinated polyetherimide. The reaction formula is as follows:

[0009]

[0010] (3) Add N,N-dimethylformamide, biphenyl diphthalonitrile, and phthalonitrile fluorinated polyetherimide into the mold, stir, heat cure at 150-400° C. for 18-21 hours, and cool to obtain a high temperature resistant and antioxidant phthalonitrile cyano resin.

[0011] Furthermore, in (1), the ratio of 4,4-biphenyl ether dianhydride, fluorine-containing aminotriazine monomer, and 2,2-bis(3-amino-4-hydroxyphenyl)propane is 1 mol:(0.567-0.633) mol:(0.05-0.15) mol.

[0012] Further, the preparation method of the fluorine-containing amino triazine monomer is as follows: nitrogen is introduced into a reaction vessel, water, acetone, 3-nitro-5-(trifluoromethyl)phenol (CAS No. 349-57-5) in a ratio of (3-3.3) mol: (3-3.3) mol: 1 mol, and sodium hydroxide are added, cyanuric chloride is added after stirring, the temperature is raised to 80-90°C, and the reaction is condensed and refluxed for 6-10 hours. After cooling, the solution is poured into ice water to precipitate a precipitate, filtered and washed with acetone, and then added to ethanol, a palladium carbon catalyst is added, hydrazine hydrate is added dropwise, heated to 75-80°C, condensed and refluxed for 12-18 hours, filtered while hot, the filtrate is cooled, the precipitate is precipitated, filtered, washed with acetone, and dried to obtain a fluorine-containing amino triazine monomer. The reaction formula is as follows:

[0013]

[0014] Furthermore, in (2), the ratio of hydroxyl fluorinated polyetherimide, potassium carbonate and 4-nitrophthalonitrile is 100 g:(2.2-7) g:(2.6-8.3) g.

[0015] Furthermore, in (3), the ratio of biphenyl type diphthalonitrile to phthalonitrile fluorinated polyetherimide is 100g:(5-20)g.

[0016] (III) The present invention has the following technical effects: a fluorinated aminotriazine monomer is used as a hyperbranched polyamine monomer, 2,2-bis(3-amino-4-hydroxyphenyl)propane is used as a diamine monomer, and 4,4-biphenyl ether dianhydride is polymerized to obtain a hyperbranched hydroxyl fluorinated polyetherimide, which contains a trifluoromethyl group and has excellent solubility in solvents such as N,N-dimethylformamide, so that the hydroxyl group can react well with 4-nitrophthalonitrile, thereby introducing a large number of phthalonitrile groups into the side chain of the polyetherimide to obtain a hyperbranched phthalonitrile fluorinated polyetherimide, which is finally co-thermally cured with biphenyl diphthalonitrile to obtain a high temperature resistant and antioxidant phthalonitrile cyano resin.

[0017] The fluorinated polyetherimide of the phthalonitrile disclosed by the invention has good solubility in solvents such as N,N-dimethylformamide, and can be blended with biphenyl-type diphthalonitrile in N,N-dimethylformamide to form a homogeneous dispersion system, so that the polyetherimide is uniformly dispersed in the biphenyl-type diphthalonitrile matrix. In addition, during the high-temperature curing process, a large number of phthalonitrile structures on the side chains of the polyetherimide can undergo a co-curing crosslinking reaction with the biphenyl-type diphthalonitrile, thereby improving the compatibility between the two and enhancing the interface bonding strength. Meanwhile, the polyetherimide contains a three-dimensional hyperbranched structure and a flexible ether bond, which can play a good toughening role and significantly improve the toughness and bending strength of the diphthalonitrile resin.

[0018] The fluorinated polyetherimide of the phthalonitrile resin contains a heat-resistant triazine ring and an imide ring, which are co-cured and cross-linked into the molecular chain of the phthalonitrile resin, thereby increasing the high-temperature mass loss temperature of the resin and showing better high-temperature resistance. After high-temperature hot air aging, the bending strength decreases slightly and has a high retention rate, showing better high-temperature resistance and antioxidant properties.

[0019] The fluorinated polyetherimide of the phthalonitrile resin contains a hydrophobic trifluoromethyl group, which is cross-linked into the molecular chain of the phthalonitrile resin to form a hydrophobic cross-linked network, which is beneficial to the hydrophobicity of the resin and reduces the water absorption rate. DETAILED DESCRIPTION

[0020] The technical solutions in the embodiments of the present invention are described clearly and completely below. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of them. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present invention.

[0021] Embodiment 1:

[0022] (1) nitrogen is introduced into a reaction vessel, 10 mL of water, 40 mL of acetone, 18 mmol of 3-nitro-5-(trifluoromethyl)phenol, and 18 mmol of sodium hydroxide are added, 6 mmol of cyanuric chloride is added after stirring, the temperature is raised to 80° C., and the reaction is condensed and refluxed for 10 h. After cooling, the solution is poured into ice water to precipitate a precipitate, which is filtered and washed with acetone, then added to 60 mL of ethanol, 0.77 g of palladium carbon catalyst is added, 25 mL of hydrazine hydrate (mass fraction 85%) is added dropwise, the reaction is heated to 75° C., the reaction is condensed and refluxed for 12 h, filtered while hot, the filtrate is cooled, a precipitate is precipitated, filtered, washed with acetone, and dried to obtain a fluorine-containing aminotriazine monomer.

[0023] (2) nitrogen was introduced into the reaction container, 40 mL of N-methylpyrrolidone, 10 mmol of 4,4-biphenyl ether dianhydride, 6 mmol of fluorine-containing aminotriazine monomer, and 1 mmol of 2,2-bis(3-amino-4-hydroxyphenyl)propane were added, and the mixture was reacted at room temperature for 18 h. After the reaction, the solution was poured onto a glass plate, and cured at 100° C. for 0.5 h, 150° C. for 1 h, 220° C. for 2 h, 260° C. for 2 h, and 300° C. for 0.5 h. The film was removed to obtain hydroxyl fluorine-containing polyetherimide.

[0024] (3) Add 300 mL of N,N-dimethylformamide and 20 g of hydroxy fluorinated polyetherimide to a reaction container, stir to dissolve (soluble), then add 0.92 g of potassium carbonate and 1.13 g of 4-nitrophthalonitrile, react at 80° C. for 12 h, cool, add water to the solution, precipitate, filter, wash with water and ethanol, and dry to obtain phthalonitrile fluorinated polyetherimide.

[0025] (4) Add 100 mL of N,N-dimethylformamide and 100 g of biphenyl diphthalonitrile (structural formula: ), 5g of phthalonitrile fluorinated polyetherimide, after stirring and dissolving (soluble), cure at 150°C for 1h, 200°C for 2h, 250°C for 2h, 300°C for 3h, 340°C for 4h, 370°C for 3h, and heat-cure at 400°C for 3h, cool to obtain a high temperature resistant and antioxidant phthalonitrile cyano resin.

[0026] Embodiment 2:

[0027] (1) nitrogen is introduced into a reaction vessel, 15 mL of water, 40 mL of acetone, 19.8 mmol of 3-nitro-5-(trifluoromethyl)phenol, and 19.8 mmol of sodium hydroxide are added, 6 mmol of cyanuric chloride is added after stirring, the temperature is raised to 90° C., and the reaction is condensed and refluxed for 6 h. After cooling, the solution is poured into ice water to precipitate a precipitate, which is filtered and washed with acetone, then added to 70 mL of ethanol, 0.72 g of palladium carbon catalyst is added, 30 mL of hydrazine hydrate (mass fraction 85%) is added dropwise, the reaction is heated to 80° C., condensed and refluxed for 18 h, filtered while hot, the filtrate is cooled, a precipitate is precipitated, filtered, washed with acetone, and dried to obtain a fluorine-containing aminotriazine monomer.

[0028] (2) nitrogen was introduced into the reaction container, 50 mL of N-methylpyrrolidone, 10 mmol of 4,4-biphenyl ether dianhydride, 5.67 mmol of fluorine-containing aminotriazine monomer, and 1.5 mmol of 2,2-bis(3-amino-4-hydroxyphenyl)propane were added, and the mixture was reacted at room temperature for 24 h. After the reaction, the solution was poured onto a glass plate, and cured at 100° C. for 1 h, 150° C. for 1 h, 220° C. for 2 h, 260° C. for 1 h, and heat-cured at 300° C. for 0.5 h. The film was removed to obtain hydroxyl fluorine-containing polyetherimide.

[0029] (3) Add 300 mL of N,N-dimethylformamide and 20 g of hydroxy fluorinated polyetherimide to a reaction container, stir to dissolve (soluble), then add 1.4 g of potassium carbonate and 1.66 g of 4-nitrophthalonitrile, react at 90° C. for 10 h, cool, add water to the solution, precipitate, filter, wash with water and ethanol, and dry to obtain fluorinated polyetherimide.

[0030] (4) Add 120 mL of N,N-dimethylformamide, 100 g of biphenyl diphthalonitrile, and 12 g of phthalonitrile fluorinated polyetherimide into the mold, stir to dissolve (soluble), and then cure at 150°C for 1 h, 200°C for 2 h, 250°C for 3 h, 300°C for 4 h, 340°C for 4 h, 370°C for 4 h, and heat cure at 400°C for 3 h, and cool to obtain a high temperature resistant and antioxidant phthalonitrile cyano resin.

[0031] Embodiment 3:

[0032] (1) Nitrogen was introduced into a reaction container, 50 mL of N-methylpyrrolidone, 10 mmol of 4,4-biphenyl ether dianhydride, 6.33 mmol of fluorine-containing aminotriazine monomer (prepared according to the method of Example 1), and 0.5 mmol of 2,2-bis(3-amino-4-hydroxyphenyl)propane were added, and the mixture was reacted at room temperature for 24 h. After the reaction, the solution was poured onto a glass plate, and cured at 100° C. for 1 h, 150° C. for 2 h, 220° C. for 2 h, 260° C. for 1 h, and heat-cured at 300° C. for 0.5 h. The film was removed to obtain a hydroxyl fluorine-containing polyetherimide.

[0033] (2) Add 250 mL of N,N-dimethylformamide and 20 g of hydroxy fluorinated polyetherimide to a reaction container, stir to dissolve (soluble), then add 0.44 g of potassium carbonate and 0.52 g of 4-nitrophthalonitrile, react at 85° C. for 6 h, cool, add water to the solution, precipitate, filter, wash with water and ethanol, and dry to obtain phthalonitrile fluorinated polyetherimide.

[0034] (3) Add 150 mL of N,N-dimethylformamide, 100 g of biphenyl diphthalonitrile, and 20 g of phthalonitrile fluorinated polyetherimide into the mold, stir to dissolve (soluble), and then cure at 150°C for 1 h, 200°C for 2 h, 250°C for 3 h, 300°C for 4 h, 340°C for 4 h, 370°C for 4 h, and 400°C for 3 h. Cool to obtain a high temperature resistant and antioxidant phthalonitrile cyano resin.

[0035] Comparative Example 1:

[0036] (1) Add 100 mL of N,N-dimethylformamide and 5 g of phthalonitrile fluorinated polyetherimide into a mold, cure at 150° C. for 1 h, cure at 200° C. for 2 h, cure at 250° C. for 2 h, cure at 300° C. for 3 h, cure at 340° C. for 4 h, cure at 370° C. for 3 h, and heat cure at 400° C. for 3 h, and cool to obtain phthalonitrile cyano resin.

[0037] Comparative Example 2:

[0038] (1) Nitrogen was introduced into the reaction vessel, and 40 mL of N-methylpyrrolidone, 10 mmol of 4,4-biphenyl ether dianhydride, and 6 mmol of 2,4,6-tris(4-aminophenoxy)-1,3,5-triazine (CAS No. 22065-34-5, structural formula: ), 1mmol 2,2-bis(3-amino-4-hydroxyphenyl)propane, react at room temperature for 18h, pour the solution onto a glass plate, cure at 100°C for 0.5h, 150°C for 1h, 220°C for 2h, 260°C for 2h, and thermally cure at 300°C for 0.5h, demold, and obtain hydroxy polyetherimide.

[0039] (2) Add 300 mL of N,N-dimethylformamide and 20 g of hydroxy polyetherimide to a reaction container, stir (undissolved), add 0.92 g of potassium carbonate and 1.13 g of 4-nitrophthalonitrile, react at 80° C. for 12 h, cool, add water to the solution, precipitate, filter, wash with water and ethanol, and dry to obtain modified polyetherimide.

[0040] (3) Add 100 mL of N,N-dimethylformamide, 100 g of biphenyl diphthalonitrile, and 5 g of modified polyetherimide into the mold, stir (not dissolved), and cure at 150°C for 1 h, 200°C for 2 h, 250°C for 2 h, 300°C for 3 h, 340°C for 4 h, 370°C for 3 h, and heat cure at 400°C for 3 h, and cool to obtain diphthalonitrile cyano resin.

[0041] Comparative Example 3:

[0042] (1) Nitrogen was introduced into the reaction vessel, and 40 mL of N-methylpyrrolidone, 10 mmol of 4,4-biphenyl ether dianhydride, and 9 mmol of 4,4'-[1,4-phenylbis(oxy)]bis[3-(trifluoromethyl)aniline] (CAS No. 22065-34-5, structural formula: ), 1mmol 2,2-bis(3-amino-4-hydroxyphenyl)propane, react at room temperature for 18h, pour the solution onto a glass plate, cure it at 100°C for 0.5h, 150°C for 1h, 220°C for 2h, 260°C for 2h, and heat cure it at 300°C for 0.5h, demold, and obtain hydroxy fluorinated polyetherimide.

[0043] (2) Add 300 mL of N,N-dimethylformamide and 20 g of hydroxy fluorinated polyetherimide to a reaction container, stir and dissolve (if soluble), then add 0.92 g of potassium carbonate and 1.13 g of 4-nitrophthalonitrile, react at 80° C. for 12 h, cool and add water to the solution to precipitate, filter and wash with water and ethanol, and dry to obtain fluorinated polyetherimide.

[0044] (3) Add 100 mL of N,N-dimethylformamide, 100 g of biphenyl diphthalonitrile, and 5 g of phthalonitrile fluorinated polyetherimide into the mold, stir (dissolved), and cure at 150°C for 1 h, 200°C for 2 h, 250°C for 2 h, 300°C for 3 h, 340°C for 4 h, 370°C for 3 h, and heat cure at 400°C for 3 h, and cool to obtain phthalonitrile cyano resin.

[0045] The phthalonitrile cyano resin was placed in a thermogravimetric analyzer and tested in nitrogen at a heating rate of 10°C / min.

[0046] Add 200 mL of water and 5 g of phthalonitrile cyano resin into a reaction container, heat to 95°C, condense and reflux for 48 hours, take out the resin, wipe off excess water on the surface, weigh it, and calculate the water absorption rate Q.

[0047] Q = (mass after water absorption - mass before water absorption) ÷ mass before water absorption × 100%.

[0048] The bending properties of phthalonitrile cyano resin were tested according to GB / T 9341-2000. The phthalonitrile cyano resin was heat treated at 300°C for 72 hours in a blast dryer, cooled to room temperature, and then tested for bending properties.

[0049] Table 1

[0050]

[0051] As can be seen from the above table, the biphenyl type diphthalonitrile of comparative example 1 has a large water absorption rate, a low 5% mass loss temperature and a low bending strength, and after high-temperature hot air aging, the bending strength decreases significantly, the retention rate is low, and the high temperature resistance and antioxidant properties are poor.

[0052] The biphenyl diphthalonitrile of Examples 1-3 is added with a fluorinated polyetherimide containing trifluoromethyl groups, which can give the polyetherimide good solubility. It has good solubility in solvents such as N,N-dimethylformamide and can be blended with the biphenyl diphthalonitrile in N,N-dimethylformamide to form a homogeneous dispersion system, so that the polyetherimide is uniformly dispersed in the biphenyl diphthalonitrile matrix. In addition, during the high-temperature curing process, a large number of phthalonitrile structures on the side chains of the polyetherimide can undergo a co-curing cross-linking reaction with the biphenyl diphthalonitrile, thereby improving the compatibility between the two and enhancing the interface bonding strength. At the same time, the polyetherimide contains a three-dimensional hyperbranched structure and a flexible ether bond, which can play a good toughening role and significantly improve the toughness and bending strength of the diphthalonitrile resin. In addition, polyetherimide contains heat-resistant triazine rings and imide rings, which are co-cured and cross-linked into the molecular chain of phthalonitrile resin, thereby increasing the 5% mass loss temperature of the resin, showing better high temperature resistance, and after high temperature hot air aging, the bending strength decreases slightly, the retention rate is high, and the high temperature resistance and antioxidant properties are very good. In addition, phthalonitrile fluorinated polyetherimide contains hydrophobic trifluoromethyl groups, which are cross-linked into the molecular chain of phthalonitrile resin to form a hydrophobic cross-linked network, which is beneficial to the hydrophobicity of the resin and reduces the water absorption rate.

[0053] Comparative Example 2 uses 2,4,6-tris(4-aminophenoxy)-1,3,5-triazine as a hyperbranched polyamine monomer, and the prepared hydroxy polyetherimide does not contain a trifluoromethyl group, has poor solubility in N,N-dimethylformamide solvent, and is difficult to effectively react with 4-nitrophthalonitrile. The side chain of the modified polyetherimide obtained does not contain a large number of phthalonitrile groups, and cannot undergo a good co-curing reaction with biphenyl-type diphthalonitrile, resulting in poor compatibility between the two, low interfacial bonding strength, poor toughening effect of polyetherimide, low bending strength of phthalonitrile resin, and high water absorption.

[0054] Comparative Example 3 uses 4,4'-[1,4-phenylbis(oxy)]bis[3-(trifluoromethyl)aniline] as a diamine monomer, and the obtained phthalonitrile fluorinated polyetherimide has good solubility in N,N-dimethylformamide, and the side chain has a large amount of phthalonitrile structure, which can co-curing crosslinking reaction with biphenyl type diphthalonitrile, improves the compatibility between the two, enhances the interface bonding strength, and is conducive to improving the toughness and bending strength of phthalonitrile resin, but its bending strength is lower than that of Example 1, mainly because the polyetherimide of Comparative Example 3 does not contain a three-dimensional hyperbranched structure, and the toughening effect is not good. And the 5% mass loss temperature is lower than that of Example 1, because the polyetherimide does not contain a heat-resistant triazine ring structure. However, the mass loss temperature is slightly higher than that of Comparative Example 2, mainly because the side chain of the polyetherimide of Comparative Example 3 contains a large amount of phthalonitrile structure, which can undergo a co-curing and cross-linking reaction with biphenyl diphthalonitrile, which is beneficial to improving the high temperature resistance of the phthalonitrile resin.

[0055] The above disclosure is only a preferred embodiment of the present invention, which certainly cannot be used to limit the scope of the present invention. Therefore, equivalent changes made according to the claims of the present invention are still within the scope of the present invention.

Claims

1. A method for preparing a high temperature resistant and antioxidant phthalonitrile cyano resin, characterized in that: The preparation method is as follows: (1) nitrogen is introduced into a reaction container, N-methylpyrrolidone, 4,4-biphenyl ether dianhydride, fluorine-containing aminotriazine monomer, and 2,2-bis(3-amino-4-hydroxyphenyl)propane are added, and after the reaction, the solution is poured onto a glass plate, thermally cured, and demolded to obtain a hydroxyl fluorine-containing polyetherimide; (2) Add N,N-dimethylformamide and hydroxy fluorinated polyetherimide to a reaction container, stir and dissolve, then add potassium carbonate and 4-nitrophthalonitrile, add water to the solution after the reaction, precipitate, filter, wash, and dry to obtain fluorinated polyetherimide; (3) Add N,N-dimethylformamide, biphenyl type diphthalonitrile, and phthalonitrile fluorinated polyetherimide into the mold, stir, heat cure, and cool to obtain a high temperature resistant and antioxidant phthalonitrile cyano resin.

2. The method for preparing the high temperature resistant and antioxidant phthalonitrile cyano resin according to claim 1, characterized in that: The reaction in (1) is carried out at room temperature for 18-24 hours; and the thermal curing is carried out at 100-300° C. for 5-7 hours.

3. The method for preparing the high temperature resistant and antioxidant phthalonitrile cyano resin according to claim 1, characterized in that: The ratio of 4,4-biphenyl ether dianhydride, fluorine-containing aminotriazine monomer and 2,2-bis(3-amino-4-hydroxyphenyl)propane in (1) is 1 mol:(0.567-0.633) mol:(0.05-0.15) mol.

4. The method for preparing the high temperature resistant and antioxidant phthalonitrile cyano resin according to claim 1, characterized in that: The preparation method of the fluorine-containing amino triazine monomer is as follows: nitrogen is introduced into a reaction container, water, acetone, 3-nitro-5-(trifluoromethyl)phenol and sodium hydroxide are added, cyanuric chloride is added after stirring, the temperature is raised to 80-90° C., condensation reflux reaction is performed for 6-10 hours, the solution is poured into ice water after cooling, a precipitate is precipitated, the precipitate is filtered and washed, and then the precipitate is added to ethanol, a palladium carbon catalyst is added, hydrazine hydrate is added dropwise, the reaction is heated to 75-80° C., condensation reflux reaction is performed for 12-18 hours, the filtrate is cooled, a precipitate is precipitated, the precipitate is filtered, washed and dried to obtain the fluorine-containing amino triazine monomer.

5. The method for preparing the high temperature resistant and oxidation resistant phthalonitrile cyano resin according to claim 4, characterized in that: The ratio of the 3-nitro-5-(trifluoromethyl)phenol, sodium hydroxide and cyanuric chloride is (3-3.3) mol: (3-3.3) mol: 1 mol.

6. The method for preparing the high temperature resistant and antioxidant phthalonitrile cyano resin according to claim 1, characterized in that: The ratio of hydroxy fluorinated polyetherimide, potassium carbonate and 4-nitrophthalonitrile in (2) is 100g:(2.2-7)g:(2.6-8.3)g.

7. The method for preparing the high temperature resistant and oxidation resistant phthalonitrile cyano resin according to claim 1, characterized in that: The reaction in (2) is carried out at 80-90°C for 6-12 hours.

8. The method for preparing the high temperature resistant and antioxidant phthalonitrile cyano resin according to claim 1, characterized in that: The ratio of biphenyl type diphthalonitrile to phthalonitrile fluorinated polyetherimide in (3) is 100g:(5-20)g.

9. The method for preparing the high temperature resistant and antioxidant phthalonitrile cyano resin according to claim 1, characterized in that: The thermal curing in (3) is carried out at 150-400° C. for 18-21 hours.

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