Phosphazene-based resin curing agent, phosphazene-based epoxy resin as well as preparation method and application of phosphazene-based epoxy resin

Abstract

The invention relates to the technical field of epoxy resin, and particularly discloses a phosphazene-based resin curing agent, phosphazene-based epoxy resin and a preparation method and application of the phosphazene-based epoxy resin. The preparation method comprises the following steps: reacting phosphonitrilic chloride trimer with fluorophenol / alcohol, double-bond-containing phenol / alcohol and an acid-binding agent to prepare a liquid intermediate product, and epoxidizing the liquid intermediate product to obtain the phosphazene-based epoxy resin; the preparation method comprises the following steps: reacting amino-containing phenol / alcohol with aldehyde to obtain a first intermediate product, reacting the first intermediate product, fluorophenol / alcohol, an acid-binding agent and phosphonitrilic chloride trimer to obtain a second intermediate product, and adding acid into the second product to obtain the phosphazene-based resin curing agent. And curing the phosphazene-based epoxy resin monomer and a phosphazene-based resin curing agent to obtain the anti-aging fluorinated epoxy resin with high phosphorus and nitrogen content. The prepared anti-aging fluorinated epoxy resin with high phosphorus and nitrogen content is excellent in comprehensive performance and has excellent thermal stability, flame retardance, aging resistance and mechanical property.

Description

Technical Field

[0001] This invention relates to the field of epoxy resin technology, and more particularly to a phosphazene-based resin curing agent, a phosphazene-based epoxy resin, its preparation method, and its application. Background Technology

[0002] Epoxy resin, as one of the most widely used thermosetting resins, boasts advantages such as excellent adhesion, chemical resistance, and high strength. However, traditional epoxy resins are flammable. To address this issue, flame-retardant additives have been developed to improve the flame-retardant properties of epoxy resins. Halogenated additives were among the earliest used flame retardants, offering advantages such as low cost and low dosage. However, during combustion, they produce hydrogen halides, brominated dibenzodioxins, and dibenzofurans, which harm human health and pollute the environment. Therefore, halogen-free flame retardants have become a research hotspot in recent years, with phosphazenes, as a material rich in phosphorus and nitrogen elements, receiving widespread attention.

[0003] Patent (CN 109734877) discloses a novel bio-based phosphazene epoxy resin monomer and the resulting bio-based phosphorus-nitrogen flame-retardant epoxy resin. The bio-based epoxy resin prepared by this method exhibits high mechanical strength and excellent flame-retardant properties. However, the regularity of its monomer molecules and the polarity of the six epoxy groups on each molecule result in poor flowability. Organic solvents need to be added during curing to improve its processing flowability. The addition of solvents limits its application in thick products, and unevaporated solvents can generate bubbles inside the product during curing, adversely affecting mechanical properties. Patent (CN 109608620) discloses a flame-retardant and biodegradable polyphosphazene epoxy resin and its preparation technology. The polyphosphazene epoxy resin prepared by this method has excellent flame retardancy and hydrophobicity, and is also biodegradable, which is beneficial to environmental protection. However, its intermediate, polydichlorophosphazene, has high reactivity and can react and crosslink with moisture in the air, requiring strict control of the reaction environment during preparation, thus demanding high preparation standards. Meanwhile, the epoxy resins prepared in these two patents still need to be cured with phosphorus-free curing agents, which means that the phosphazene content of the final product cannot be further increased, limiting the further enhancement of the product's heat resistance, aging resistance, and flame retardant properties. Summary of the Invention

[0004] To address the issue that the mechanical properties, heat resistance, aging resistance, and flame retardant properties of flame-retardant epoxy resins in existing technologies need further improvement, this invention provides a phosphazene-based resin curing agent, a phosphazene-based epoxy resin, its preparation method, and its applications.

[0005] To solve the above-mentioned technical problems, the technical solution provided by the present invention is as follows:

[0006] In a first aspect, the present invention provides a phosphazene-based resin curing agent, the structural formula of which is shown in formula (Ⅰ):

[0007]

[0008] Where m is an integer from 1 to 6;

[0009] R2 is selected from C2 to C10 fluorinated alkyl groups, fluorinated phenyl groups, or fluorinated alkylphenyl groups; wherein the fluorinated alkyl group contains two or more fluorine atoms;

[0010] R4 is selected from phenyl, nitrophenyl, cyclohexyl, adamantyl, or C2-C5 alkyl groups.

[0011] Compared to existing technologies, the phosphazene-based resin curing agent provided by this invention introduces fluorine-containing substituents into the cyclophosphonitrile skeleton structure. On the one hand, the fluorine shielding effect formed by multiple fluorine atoms in the fluorine-containing substituents can greatly reduce the possibility of molecular oxidation and hydrolysis; on the other hand, the fluorine-containing substituents can significantly enhance the stability of the cyclophosphonitrile structure, effectively resisting the damage of strong corrosive media such as acids and alkalis, and effectively extending the service life of the resin material. The fluorine-containing structure in R2 can reduce the cohesive energy density of the molecular chain, reduce the frictional heat generation between molecules, and improve the heat resistance of the material. The introduction of the sterically hindered group in R4 can restrict the thermal motion of the molecular chain, increase the rigidity of the molecular chain, and further increase the thermal decomposition temperature of the cured product. At the same time, the sterically hindered group acts as a physical cross-linking point in the molecule, enhancing the interaction between molecular chains, so that the cured resin material has good hardness and mechanical properties. In addition, this phosphazene-based resin curing agent exhibits good compatibility when mixed and cured with different types of resins, and has broad application prospects.

[0012] It should be noted that the substituents containing R2 and R4 in this invention are all substituents on the P atoms of the six-membered ring, with two substituents on each P atom.

[0013] Furthermore, R2 is selected from the following groups:

[0014]

[0015] Furthermore, R4 is selected from the following groups:

[0016]

[0017] In this context, * indicates the position where the group is attached to the N atom.

[0018] The preferred R2 and R4 substituents are beneficial to improving the thermal stability, corrosion resistance, hardness and mechanical properties of the curing agent, thus meeting the market requirements for high-performance resin curing agents.

[0019] Secondly, the present invention provides a method for preparing a phosphazene-based resin curing agent, comprising the following steps:

[0020] S1, condensation reaction of aminophenol / alcohol compound NH2-R4-OH and aldehyde substance R3-CHO to obtain intermediate 1 as shown in formula (II);

[0021]

[0022]

[0023] S2, under acid-binding conditions, hexachlorocyclophosphamide, fluorophenol / alcohol compound R2-OH and intermediate 1 undergo a substitution reaction to obtain intermediate 2 as shown in formula (Ⅲ);

[0024]

[0025] S3, the intermediate 2 is hydrolyzed under acidic conditions to obtain the phosphazene-based resin curing agent shown in formula (Ⅰ).

[0026] The method for preparing phosphazene-based resin curing agents provided by this invention has a simple reaction route, readily available raw materials, and is easy to promote and apply in industrial production. The method has high adaptability and can prepare phosphazene-based resin curing agents with diverse structures and properties, thus broadening the application range of the products and meeting the diverse market demand for high-performance resin curing agents.

[0027] Further, in S1, the aminophenol / alcohol-containing compound is at least one of p-aminophenol, m-aminophenol, o-aminophenol, 2-amino-4-nitrophenol, 2-aminocyclohexanol, 3-aminoadamantanol, or isopropanolamine.

[0028] Further, in S1, the aldehyde substance is at least one of formaldehyde, acetaldehyde, furfural, decanal, n-butyraldehyde, n-propionaldehyde, benzaldehyde, undecylaldehyde, dodecaaldehyde, pentadecylaldehyde, theobromaldehyde, isobutyraldehyde, isovaleraldehyde, cinnamaldehyde, or cinnamaldehyde.

[0029] Furthermore, in S1, the condensation reaction takes place at a temperature of 50°C to 70°C.

[0030] Furthermore, in S1, the molar ratio of the aminophenol / alcohol compound to the aldehyde is 1:(1-3).

[0031] Specifically, in S1, the reaction solvent is one or more of dimethylformamide, dimethylacetamide, tetrahydrofuran, dimethyl sulfoxide, xylene, or ethyl acetate.

[0032] Specifically, in S1, the ratio of the aminophenol / alcohol compound to the above reaction solvent is 1g:(1-10)mL.

[0033] Specifically, in S1, after the condensation reaction is completed, the reaction solution is added to a precipitant, the solid and liquid are separated, and the solution is dried to obtain intermediate 1.

[0034] In conjunction with the above, in S1, the precipitant is one or both of petroleum ether or anhydrous ethanol.

[0035] Specifically, in S1, the volume ratio of the condensation reaction solution to the precipitant is 1:(0.5-10).

[0036] Further, in S2, the fluoroethanol / phenol compound includes at least one of difluoroethanol, trifluoroethanol, tetrafluoropropanol, pentafluoropropanol, hexafluoroisopropanol, hexafluorobutanol, heptafluorobutanol, heptafluoropentanol, octafluoropentanol, nonafluoropentanol, nonafluorohexanol, dodecafluoroheptanol, p-trifluoromethylphenol, m-trifluoromethylphenol, o-trifluoromethylphenol, 4-ethyl-2,6-difluorophenol, 2-ethyl-4-fluorophenol, 3-ethyl-4-fluorophenol, 4-fluorophenol, and 2-fluorophenol.

[0037] Furthermore, in this S2, the acid-binding agent is at least one of calcium carbonate, potassium carbonate, cesium carbonate, triethylamine, sodium metal, sodium hydride, or potassium metal.

[0038] Further, in S2, the molar ratio of the hexachlorocyclophosphamide, the fluoroalcohol / phenol compound, the intermediate product 1 and the acid-binding agent is 1:(3-6):(2-4):(6-8).

[0039] Specifically, in S2, the reaction solvent is one or more of dimethylformamide, dimethylacetamide, tetrahydrofuran, dimethyl sulfoxide, dichloromethane, xylene, ethyl acetate, chloroform, or chloroform.

[0040] Specifically, in S2, the ratio of the hexachlorocyclophosphine to the above reaction solvent is 1g:(1~10)mL.

[0041] As a specific embodiment of the present invention, S2 specifically includes the following steps:

[0042] Hexachlorocyclophosphonitrile, fluoroalcohol / phenol compound, intermediate 1, and acid-binding agent were mixed evenly in a reaction solvent at -25℃ to 0℃ and stirred for 1h to 6h. The temperature was then raised to 25℃ to 120℃ and stirred for 24h to 72h. After the reaction was completed, the mixture was cooled to 20℃ to 30℃. A precipitating agent was added to the reaction solution, and the solid and liquid were separated. The precipitate was dried to obtain intermediate 2.

[0043] In summary, the precipitant is one or more of water, anhydrous ethanol, or petroleum ether.

[0044] Specifically, in S2, the volume ratio of the reaction solution to the precipitant is 1:(1~10).

[0045] As a specific embodiment of the present invention, S3 specifically includes the following steps:

[0046] Intermediate 2 is added to an organic solvent, followed by an acid solution. The mixture is reacted at 10°C to 100°C for 1 to 3 hours. After the reaction is complete, the reaction solution is added to a precipitant, and the solid and liquid are separated to obtain a precipitate. The above hydrolysis process is repeated 1 to 5 times, and the precipitate is dried to obtain a phosphazene-based resin curing agent.

[0047] In combination with the above, in S3, the ratio of intermediate 2 to organic solvent is 1g:(1~10)mL.

[0048] In conjunction with the above, in S3, the acid solution is one or more of hydrochloric acid, nitric acid, sulfuric acid, hypochlorous acid, or acetic acid.

[0049] Specifically, in S3, an acid solution is added until the pH of the system is 5 to 7.

[0050] In conjunction with the above, in S3, the precipitant is one or more of water, anhydrous ethanol, or petroleum ether.

[0051] Specifically, in S3, the volume ratio of the reaction solution to the precipitant is 1:(1~10).

[0052] Thirdly, the present invention provides a method for preparing a phosphazene-based epoxy resin, comprising the following steps:

[0053] Step a: Under acid-binding agent conditions, hexachlorocyclotriphosphazene, double-bonded alcohol / phenol compound R1-OH and fluorinated alcohol / phenol compound R2-OH react to obtain intermediate a shown;

[0054]

[0055] Step b: The intermediate a is added to an oxidant solution to carry out an oxidation reaction, thereby obtaining a phosphazene-based epoxy resin.

[0056] Compared to existing technologies, the method for preparing aging-resistant phosphazene-based epoxy resin provided by this invention uses hexachlorocyclotriphosphazene as the basic skeleton. Double bonds are introduced into the basic skeleton through double-bonded alcohol / phenol compounds, which can be further cross-linked and cured in subsequent oxidation reactions, enhancing the density of the molecular network, reducing the damage of external factors to the resin molecular chains, and improving the anti-aging ability. By introducing multiple fluorine atoms into the basic skeleton through fluorinated alcohol / phenol compounds, the epoxy resin's barrier ability against aging media such as oxygen and water vapor is significantly enhanced, greatly delaying the aging process of the resin.

[0057] Specifically, step a includes the following steps:

[0058] Hexachlorocyclophosphonitrile, fluorophenol / alcohol compound and acid-binding agent were added to the reaction solvent at -20℃ to 5℃ and mixed evenly. The mixture was stirred for 0.5h to 6h, then heated to 60℃ to 120℃ and stirred for 12h to 72h. After the reaction was completed, the reaction solution was added to the precipitant, the solid and liquid were separated, and the precipitate was dried to obtain intermediate a.

[0059] In conjunction with the above, in step a, the reaction solvent is one or more of dimethylformamide, dimethylacetamide, tetrahydrofuran, dimethyl sulfoxide, dichloromethane, or chloroform.

[0060] Further, in step a, the ratio of hexachlorocyclophosphamide to the reaction solvent is 1 g: (1-10) mL.

[0061] Further, in step a, the double-bonded alcohol / phenol compound includes at least one of ethylene glycol monovinyl ether, 2-methyl-3-buten-2-ol, eugenol, cashew phenol, 4-allylphenol, or terpineol.

[0062] Further, in step a, the fluoroalcohol / phenol compound includes at least one of difluoroethanol, trifluoroethanol, tetrafluoropropanol, pentafluoropropanol, hexafluoroisopropanol, hexafluorobutanol, heptafluorobutanol, heptafluoropentanol, octafluoropentanol, nonafluoropentanol, nonafluorohexanol, dodecafluoroheptanol, p-trifluoromethylphenol, m-trifluoromethylphenol, o-trifluoromethylphenol, 4-ethyl-2,6-difluorophenol, 2-ethyl-4-fluorophenol, 3-ethyl-4-fluorophenol, 4-fluorophenol, and 2-fluorophenol.

[0063] Further, in step a, the acid-binding agent is at least one of calcium carbonate, potassium carbonate, cesium carbonate, triethylamine, sodium metal, sodium hydride, or potassium metal.

[0064] Further, in step a, the molar ratio of the hexachlorocyclotriphosphazene, fluorophenol / alcohol compound, double-bonded phenol / alcohol compound and acid-binding agent is 1:(3-6):(2-4):(6-8).

[0065] Further, in step a, the precipitant is one or two of water, anhydrous ethanol, or petroleum ether.

[0066] Furthermore, in step a, the volume ratio of the reaction solution to the precipitant is 1:(1-10).

[0067] Further, in step b, the oxidant in the oxidant solution is selected from one or more of m-chloroperoxybenzoic acid, hydrogen peroxide, peracetic acid, peroxybenzoic acid, tert-butanol hydrogen peroxide, and cumene hydrogen peroxide; the solvent is selected from one or more of dimethylformamide, dimethylacetamide, tetrahydrofuran, dimethyl sulfoxide, dichloromethane, and chloroform.

[0068] Furthermore, in step b, the ratio of intermediate a to the solvent in the oxidant solution is 1 g: (1-15) mL.

[0069] Furthermore, in step b, the molar ratio of the oxidant to intermediate a is (1.5–9):1.

[0070] Furthermore, in step b, the oxidation reaction is carried out at a temperature of 30°C to 60°C for 3 hours to 15 hours.

[0071] It should be noted that in step b, after the oxidation reaction is complete, the reaction solution is added to a precipitant, the solid and liquid are separated, and the precipitate is dried to obtain phosphazene-based epoxy resin. Specifically, the precipitant is petroleum ether or anhydrous ethanol.

[0072] Fourthly, the present invention also provides a phosphazene-based epoxy resin, which is prepared by the method for preparing the phosphazene-based epoxy resin.

[0073] Fifthly, the present invention also provides an aging-resistant fluorinated epoxy resin, which is prepared by curing the phosphazene-based epoxy resin and the phosphazene-based resin curing agent described in any one of the above claims.

[0074] Furthermore, using the phosphazene-based resin curing agent prepared above as a curing agent, its active functional groups can react efficiently with the epoxy groups in the epoxy resin, promoting the formation of a denser and more uniform cross-linked structure between molecular chains. Compared with ordinary curing agents, the unique molecular structure of the phosphazene-based resin curing agent can make the cross-linking points more rationally distributed, avoiding the problem of excessive or insufficient local cross-linking. This optimized cross-linking structure not only enhances the mechanical strength and impact resistance of the material, but also improves the overall stability of the material, enabling it to better maintain structural integrity when subjected to external forces or environmental changes, and reducing the risk of aging caused by structural defects.

[0075] Specifically, the preparation method of the above-mentioned aging-resistant fluorinated epoxy resin includes the following steps:

[0076] The above-mentioned phosphazene-based resin curing agent is added to the phosphazene-based epoxy resin and cured to obtain an aging-resistant phosphazene-based epoxy resin.

[0077] Furthermore, the mass ratio of the phosphazene-based epoxy resin to the phosphazene-based resin curing agent is (10-30):(5-20).

[0078] Furthermore, a staged curing method is adopted, wherein the curing temperature of the first stage is 60℃~80℃ and the curing time is 1h~2h; the curing temperature of the second stage is 90℃~100℃ and the curing time is 1h~3h; the curing temperature of the third stage is 120℃~150℃ and the curing time is 2h~3h; and the curing temperature of the fourth stage is 180℃~200℃ and the curing time is 1h~2h.

[0079] Sixthly, the present invention also provides the application of the above-mentioned aging-resistant fluorinated epoxy resin in the field of electronic packaging materials.

[0080] In summary, the aging-resistant fluorinated epoxy resin provided by this invention has the following beneficial effects:

[0081] (1) The aging-resistant fluorinated epoxy resin of the present invention is a resin containing three flame-retardant elements: phosphorus, nitrogen, and fluorine, which is cured by phosphazene-based epoxy resin and phosphazene-based resin curing agent. Among them, phosphorus is used as an acid source, fluorine and nitrogen are used as gas sources, and the side groups on the phosphazene ring are used as carbon sources. It can form a good expanding carbon layer, which can protect the lower matrix and prevent the flame from damaging the lower matrix. At the same time, phosphorus and fluorine generate phosphate free radicals and organofluorine free radicals under the action of flame, which can capture hydrogen free radicals and hydroxyl free radicals, prevent the free radical chain reaction process, and make it have excellent flame-retardant properties.

[0082] (2) The epoxy resin of the present invention contains fluorine, which has excellent hydrophobic, oil-resistant and solvent-resistant properties. At the same time, fluorine has the characteristic of migrating to the surface of the material, which will cause the flame retardant to migrate to the surface of the material as the service time increases, and reduce the hydrophobic, oil-resistant and solvent-resistant properties of the material after wear. However, the fluorine in the present invention is covalently linked to the phosphazene-based epoxy resin and the phosphazene-based resin curing agent, and is uniformly distributed in the material after curing. Due to the presence of covalent bonds, the migration of fluorine is restricted, so that even if it is worn during use, it can still maintain good hydrophobic, oil-resistant and solvent-resistant properties.

[0083] (3) Thanks to the presence of rigid phosphazene rings, benzene rings and flexible alkoxy chains in the phosphazene-based epoxy resin and phosphazene-based resin curing agent, the aging-resistant fluorinated epoxy resin of the present invention has both high strength and high toughness.

[0084] (4) The bond energy of CF bond is higher than that of CH bond and CO bond. Under aging conditions such as heat, light and oxygen, it can effectively resist molecular chain breakage and oxidative degradation. The high electronegativity of fluorine atom and the steric hindrance form the "fluorine shell" structure, which can shield the epoxy resin backbone, reduce free radical attack and direct damage from ultraviolet rays. In addition, due to its excellent hydrophobic properties, it can reduce the penetration of water and corrosive media, thereby inhibiting humid heat aging, hydrolysis and electrochemical corrosion, which is beneficial to improving the aging resistance of resin.

[0085] (5) The phosphazene-based epoxy resin and phosphazene-based resin curing agent of the present invention have good fluidity at 25 to 80°C, can be processed and molded without the addition of solvents or diluents, have good processing performance, and reduce the emission of organic VOCs. Detailed Implementation

[0086] To make the objectives, technical solutions, and advantages of this invention clearer, the invention will be further described in detail below with reference to embodiments. It should be understood that the specific embodiments described herein are merely illustrative and not intended to limit the invention.

[0087] Unless otherwise specified, all reagents used in the following embodiments are commercially available analytical grade reagents, and all experimental and detection methods used in the following embodiments are existing experimental and detection methods.

[0088] To better illustrate the present invention, further examples are provided below.

[0089] Example 1

[0090] I. This embodiment provides a phosphazene-based epoxy resin:

[0091] Step A1: Hexachlorocyclotriphosphazene (1 mol), trifluoroethanol (4 mol), 4-allylphenol (2 mol), and sodium hydride (6 mol) were added to tetrahydrofuran (THF) (1800 mL). The mixture was reacted at -10 °C for 2 h, then heated to 100 °C and reacted for 5 h. After the reaction was completed, the mixture was cooled to 25 °C, and the reaction solution was added to water (25000 mL). The precipitate was dried to obtain a liquid intermediate product with the following structural formula:

[0092]

[0093] n is an integer from 1 to 6;

[0094] Step A2: Add the liquid intermediate product (1 mol) and tert-butanol hydrogen peroxide (2 mol) to THF (1000 mL), heat to 40 °C and react for 6 h. After the reaction is complete, cool to room temperature, filter, evaporate and concentrate the filtrate, filter again, and dry the filtrate to obtain phosphazene-based epoxy resin with the following structural formula:

[0095]

[0096] n is an integer from 1 to 6.

[0097] II. This embodiment provides a phosphazene-based resin curing agent:

[0098] Step B1: Add 1 mol of p-aminophenol and 2 mol of n-butyraldehyde to dimethylacetamide (DMA) (500 ml), react at 60 °C for 3 hours, cool to room temperature, add 2000 ml of ethanol to precipitate, and dry to obtain the first intermediate product, with the following structural formula:

[0099]

[0100] Step B2: Hexachlorocyclotriphosphazene (1 mol), trifluoroethanol (5 mol), the first intermediate (3 mol), and triethylamine (6 mol) were added to dimethylformamide (600 mL). The mixture was reacted at -20 °C for 1 h, then heated to 110 °C and reacted for 30 h. After the reaction was completed, the mixture was cooled to 30 °C, and the reaction solution was added to petroleum ether (6000 mL). The precipitate was dried to obtain the second intermediate, with the following structural formula:

[0101]

[0102] m is an integer from 1 to 6;

[0103] Step B3: Dissolve the second intermediate (100g) in THF (500mL), add sulfuric acid to adjust the solution pH to 5, react at 60℃ for 2h, add water (2000mL) to precipitate, repeat the operation twice, dry the precipitate to obtain the phosphazene-based resin curing agent, with the following structural formula:

[0104]

[0105] m is an integer from 1 to 6.

[0106] III. This embodiment provides an aging-resistant fluorinated epoxy resin:

[0107] The phosphazene-based epoxy resin (25g) and phosphazene-based resin curing agent (12g) prepared above were mixed and cured at 90°C for 1h, 110°C for 2h, 150°C for 2h, and 180°C for 1h to obtain an aging-resistant fluorinated epoxy resin.

[0108] Example 2

[0109] I. This embodiment provides a phosphazene-based epoxy resin:

[0110] Step A1: 1 mol of hexachlorocyclotriphosphazene, 6 mol of tetrafluoropropanol, 3 mol of eugenol, and 8 mol of metallic sodium were added to chloroform (2500 mL). The mixture was reacted at -15°C for 4 h, then heated to 95°C and reacted for 6 h. After the reaction was completed, the mixture was cooled to 25°C, and the reaction solution was added to 5000 mL of ethanol. The precipitate was dried to obtain a liquid intermediate product with the following structural formula:

[0111]

[0112] n is an integer from 1 to 6;

[0113] Step A2: Add the liquid intermediate product (1 mol) and cumene hydroperoxide (3 mol) prepared above to chloroform (2000 mL), heat to 60 °C and react for 10 h. After the reaction is complete, cool to room temperature, filter, evaporate and concentrate the filtrate, filter again, and dry the filtrate to obtain phosphazene-based epoxy resin with the following structural formula:

[0114]

[0115] n is an integer from 1 to 6.

[0116] II. This embodiment provides a phosphazene-based resin curing agent:

[0117] Step B1: Add m-aminophenol (1 mol) and benzaldehyde (2 mol) to DMF (2200 mL), react at 50 °C for 5 h, cool to room temperature, and add ethanol (5000 mL) to precipitate, obtaining the first intermediate product with the following structural formula:

[0118]

[0119] Step B2: Hexachlorocyclotriphosphazene (1 mol), tetrafluoropropanol (6 mol), the first intermediate (4 mol), and sodium hydride (7 mol) were added to THF (1500 mL). The mixture was reacted at -25 °C for 2 h, then heated to 67 °C and reacted for 72 h. After the reaction was completed, the mixture was cooled to 30 °C, and the reaction solution was added to water (4500 mL). The precipitate was dried to obtain the second intermediate, with the following structural formula:

[0120]

[0121] m is an integer from 1 to 6;

[0122] Step B3: Dissolve the second intermediate (100g) in dichloromethane (DCM) (800mL), add acetic acid to adjust the solution pH to 7, react at 30℃ for 3h, add ethanol (3000mL) to precipitate, repeat the operation 5 times, dry the precipitate to obtain the phosphazene-based resin curing agent, with the following structural formula:

[0123]

[0124] m is an integer from 1 to 6.

[0125] III. This embodiment provides an aging-resistant fluorinated epoxy resin:

[0126] The phosphazene-based epoxy resin (30g) and phosphazene-based resin curing agent (15g) prepared above were mixed and cured at 60°C for 1h, 100°C for 3h, 150°C for 2h, and 200°C for 1h to obtain an aging-resistant fluorinated epoxy resin.

[0127] Example 3

[0128] I. This embodiment provides a phosphazene-based epoxy resin:

[0129] Step A1: Hexachlorocyclotriphosphazene (1 mol), hexafluoroisopropanol (5 mol), eugenol (3 mol), and sodium hydride (7 mol) were added to dimethyl sulfoxide (DMSO) (800 mL). The mixture was reacted at -18 °C for 4 h, then heated to 90 °C and reacted for 8 h. After the reaction was completed, the mixture was cooled to 25 °C, and the reaction solution was added to petroleum ether (5500 mL). The precipitate was dried to obtain a liquid intermediate product with the following structural formula:

[0130]

[0131] n is an integer from 1 to 6;

[0132] Step A2: Add the liquid intermediate (1 mol) and benzoic acid peroxide (4 mol) to DMSO (1000 mL), heat to 50 °C and react for 12 h. After the reaction is complete, cool to room temperature, filter, evaporate and concentrate the filtrate, filter again, and dry the filtrate to obtain phosphazene-based epoxy resin with the following structural formula:

[0133]

[0134] n is an integer from 1 to 6.

[0135] II. This embodiment provides a phosphazene-based resin curing agent:

[0136] Step B1: 1 mol of o-aminophenol and 2 mol of decanal were reacted in 500 mL of dimethylformamide (DMF) at 55 °C for 5 h. After cooling to room temperature, 4000 mL of petroleum ether was added to precipitate the product. The product was dried to obtain the first intermediate product, with the following structural formula:

[0137]

[0138] Step B2: Hexachlorocyclotriphosphazene (1 mol), hexafluoroisopropanol (5 mol), the first intermediate (2 mol), and sodium hydride (7 mol) were added to THF (2000 mL). The mixture was reacted at -25 °C for 6 h, then heated to 95 °C and reacted for 50 h. After the reaction was completed, the mixture was cooled to 20 °C, and the reaction solution was added to ethanol (3000 mL). The precipitate was dried to obtain the second intermediate, with the following structural formula:

[0139]

[0140] m is an integer from 1 to 6;

[0141] Step B3: Dissolve the second intermediate (100g) in DMSO (800mL), add nitric acid to bring the solution pH to 5.5, react at 85℃ for 3h, add petroleum ether (5000mL) to precipitate, repeat the operation once, dry the precipitate to obtain the phosphazene-based resin curing agent, with the following structural formula:

[0142]

[0143] m is an integer from 1 to 6.

[0144] III. This embodiment provides an aging-resistant fluorinated epoxy resin:

[0145] The phosphazene-based epoxy resin (25g) and phosphazene-based resin curing agent (12g) prepared above were mixed and cured at 70°C for 2h, 110°C for 2h, 160°C for 3h, and 190°C for 1h to obtain an aging-resistant fluorinated epoxy resin.

[0146] Example 4

[0147] I. This embodiment provides a phosphazene-based epoxy resin:

[0148] Step A1: 1 mol of hexachlorocyclotriphosphazene, 4 mol of nonafluoropentanol, 3 mol of cashew nut shell powder, and 6 mol of metallic sodium were added to 1700 mL of DCM. The mixture was reacted at -10 °C for 3 h, then heated to 30 °C and reacted for 15 h. After the reaction was complete, the mixture was cooled to 20 °C, and the reaction solution was added to 7000 mL of petroleum ether. The precipitate was dried to obtain a liquid intermediate product with the following structural formula:

[0149]

[0150] n is an integer from 1 to 6;

[0151] Step A2: Add the prepared liquid intermediate (1 mol) and peroxybenzoic acid (3 mol) to DCM (5400 mL), heat to 30 °C and react for 9 h. After the reaction is complete, cool to room temperature, filter, evaporate and concentrate the filtrate, filter again, and dry the filtrate to obtain phosphazene-based epoxy resin with the following structural formula:

[0152]

[0153] n is an integer from 1 to 6.

[0154] II. This embodiment provides a phosphazene-based resin curing agent:

[0155] Step B1: Add m-aminophenol (1 mol) and decanal (3 mol) to DMA (800 mL), react at 65 °C for 6 h, cool to room temperature, add ethanol (5000 mL) to precipitate, and dry to obtain the first intermediate product, with the following structural formula:

[0156]

[0157] Step B2: Hexachlorocyclotriphosphazene (1 mol), nonafluoropentanol (4 mol), the first intermediate (3 mol), and sodium hydride (7 mol) were added to DMF (1500 mL). The mixture was reacted at -20 °C for 2 h, then heated to 100 °C and reacted for 40 h. After the reaction was completed, the mixture was cooled to 25 °C, and the reaction solution was added to ethanol (3000 mL). The precipitate was dried to obtain the second intermediate, with the following structural formula:

[0158]

[0159] m is an integer from 1 to 6;

[0160] Step B3: Dissolve the second intermediate (100g) in DMF (900mL), add sulfuric acid to adjust the solution pH to 6.5, react at 90℃ for 2h, add petroleum ether (3000mL) to precipitate, repeat the operation 5 times, dry the precipitate to obtain the phosphazene-based resin curing agent, with the following structural formula:

[0161]

[0162] m is an integer from 1 to 6.

[0163] III. This embodiment provides an aging-resistant fluorinated epoxy resin:

[0164] The phosphazene-based epoxy resin (20g) and phosphazene-based resin curing agent (12g) prepared above were mixed and cured at 60°C for 2h, 100°C for 3h, 150°C for 3h, and 180°C for 2h to obtain an aging-resistant fluorinated epoxy resin.

[0165] Example 5

[0166] I. This embodiment provides a phosphazene-based epoxy resin:

[0167] Step A1: Hexachlorocyclotriphosphazene (1 mol), pentafluoropropanol (5 mol), eugenol (2 mol), and metallic potassium (6 mol) were added to DMSO (1900 mL). The mixture was reacted at -18 °C for 4 h, then heated to 85 °C and reacted for 9 h. After the reaction was completed, the mixture was cooled to 20 °C, and the reaction solution was added to ethanol (15000 mL). The precipitate was dried to obtain a liquid intermediate product with the following structural formula:

[0168]

[0169] n is an integer from 1 to 6;

[0170] Step A2: Add the liquid intermediate product (1 mol) and cumene hydroperoxide (6 mol) prepared above to DMSO (2000 mL), heat to 60 °C and react for 12 h. After the reaction is complete, cool to room temperature, filter, evaporate and concentrate the filtrate, filter again, and dry the filtrate to obtain phosphazene-based epoxy resin with the following structural formula:

[0171]

[0172] n is an integer from 1 to 6.

[0173] II. This embodiment provides a phosphazene-based resin curing agent:

[0174] Step B1: 1 mol of 2-amino-4-nitrophenol and 2 mol of n-butyraldehyde were added to DMA (700 mL), and the mixture was reacted at 55 °C for 5 h. After cooling to room temperature, 5000 mL of petroleum ether was added to precipitate the product, and the product was dried to obtain the first intermediate product, with the following structural formula:

[0175]

[0176] Step B2: Hexachlorocyclotriphosphazene (1 mol), pentafluoropropanol (5 mol), the first intermediate (2 mol), and sodium hydride (7 mol) were added to DCM (1800 mL). The mixture was reacted at -25 °C for 3 h, then heated to 95 °C and reacted for 48 h. After the reaction was completed, the mixture was cooled to 20 °C, and the reaction solution was added to ethanol (14000 mL). The precipitate was dried to obtain the second intermediate, with the following structural formula:

[0177]

[0178] m is an integer from 1 to 6;

[0179] Step B3: Dissolve the second intermediate (100g) in DMSO (200mL), add acetic acid to bring the solution pH to 5.8, react at 85℃ for 3h, add petroleum ether (2000mL) to precipitate, repeat the operation 4 times, dry the precipitate to obtain the phosphazene-based resin curing agent, with the following structural formula:

[0180]

[0181] m is an integer from 1 to 6.

[0182] III. This embodiment provides an aging-resistant fluorinated epoxy resin:

[0183] The phosphazene-based epoxy resin (30g) and phosphazene-based resin curing agent (15g) prepared above were mixed and cured at 70°C for 2h, 110°C for 2h, 150°C for 3h, and 180°C for 1h to obtain an aging-resistant fluorinated epoxy resin.

[0184] Example 6

[0185] I. This embodiment provides a phosphazene-based epoxy resin:

[0186] Step A1: Hexachlorocyclotriphosphazene (1 mol), tetrafluoropropanol (5 mol), cashew nut shell powder (3 mol), and metallic sodium (6 mol) were added to DCM (850 mL). The mixture was reacted at -15 °C for 2 h, then heated to 90 °C and reacted for 8 h. After the reaction was completed, the mixture was cooled to 20 °C, and the reaction solution was added to petroleum ether (7000 mL). The precipitate was dried to obtain a liquid intermediate product with the following structural formula:

[0187]

[0188] n is an integer from 1 to 6;

[0189] Step A2: Add the liquid intermediate (1 mol) and tert-butanol hydrogen peroxide (3 mol) to DCM (1000 mL), heat to 50 °C and react for 10 h. After the reaction is complete, cool to room temperature, filter, evaporate and concentrate the filtrate, filter again, and dry the filtrate to obtain phosphazene-based epoxy resin with the following structural formula:

[0190]

[0191] n is an integer from 1 to 6.

[0192] II. This embodiment provides a phosphazene-based resin curing agent:

[0193] Step B1: 1 mol of 3-aminoadamantanol and 2 mol of benzaldehyde were added to DMA (1500 mL), and the mixture was reacted at 60 °C for 4 h. After cooling to room temperature, 10000 mL of petroleum ether was added to precipitate the product, and the product was dried to obtain the first intermediate product, with the following structural formula:

[0194]

[0195] Step B2: Hexachlorocyclotriphosphazene (1 mol), tetrafluoropropanol (5 mol), the first intermediate (2 mol), and metallic potassium (7 mol) were added to THF (700 mL). The mixture was reacted at -20 °C for 4 h, then heated to 95 °C and reacted for 36 h. After the reaction was completed, the mixture was cooled to 20 °C, and the reaction solution was added to petroleum ether (7000 mL). The precipitate was dried to obtain the second intermediate, with the following structural formula:

[0196]

[0197] m is an integer from 1 to 6;

[0198] Step B3: Dissolve the second intermediate (100g) in DMA (700mL), add nitric acid to bring the solution pH to 5.5, react at 80℃ for 2 hours, add petroleum ether (2000mL) to precipitate, repeat the operation once, dry the precipitate to obtain the phosphazene-based resin curing agent, with the following structural formula:

[0199]

[0200] m is an integer from 1 to 6.

[0201] III. This embodiment provides an aging-resistant fluorinated epoxy resin:

[0202] The phosphazene-based epoxy resin (20g) and phosphazene-based resin curing agent (10g) prepared above were mixed and cured at 60°C for 1h, 100°C for 2h, 150°C for 2h, and 180°C for 1h to obtain an aging-resistant fluorinated epoxy resin.

[0203] Example 7

[0204] I. This embodiment provides a phosphazene-based epoxy resin:

[0205] Step A1: 1 mol of hexachlorocyclotriphosphazene, 5 mol of hexafluoroisopropanol, 3 mol of 4-allylphenol, and 8 mol of sodium hydride were added to 1200 mL of DCM. The mixture was reacted at -10 °C for 5 h, then heated to 90 °C and reacted for 10 h. After the reaction was complete, the mixture was cooled to 20 °C, and the reaction solution was added to 5500 mL of ethanol. The precipitate was dried to obtain a liquid intermediate with the following structural formula:

[0206]

[0207] n is an integer from 1 to 6;

[0208] Step A2: Add the prepared liquid intermediate (1 mol) and peroxybenzoic acid (3 mol) to DCM (3000 mL), heat to 60 °C and react for 12 h. After the reaction is complete, cool to room temperature, filter, evaporate and concentrate the filtrate, filter again, and dry the filtrate to obtain phosphazene-based epoxy resin with the following structural formula:

[0209]

[0210] n is an integer from 1 to 6.

[0211] II. This embodiment provides a phosphazene-based resin curing agent:

[0212] Step B1: 1 mol of 2-aminocyclohexanol and 2 mol of decanal were added to 600 mL of DMF and reacted at 65 °C for 6 h. After cooling to room temperature, 6000 mL of petroleum ether was added to precipitate the product, and the product was dried to obtain the first intermediate product, with the following structural formula:

[0213]

[0214] Step B2: Hexachlorocyclotriphosphazene (1 mol), hexafluoroisopropanol (5 mol), the first intermediate (2 mol), and sodium hydride (7 mol) were added to DMA (2000 mL). The mixture was reacted at -25 °C for 3 h, then heated to 95 °C and reacted for 48 h. After the reaction was completed, the mixture was cooled to 20 °C, and the reaction solution was added to petroleum ether (16000 mL). The precipitate was dried to obtain the second intermediate, with the following structural formula:

[0215]

[0216] m is an integer from 1 to 6;

[0217] Step B3: Dissolve the second intermediate (100g) in DMA (950mL), add hydrochloric acid to bring the solution pH to 6, react at 85℃ for 3h, add petroleum ether (2000mL) to precipitate, repeat the operation once, dry the precipitate to obtain the phosphazene-based resin curing agent, with the following structural formula:

[0218]

[0219] m is an integer from 1 to 6.

[0220] III. This embodiment provides an aging-resistant fluorinated epoxy resin:

[0221] The phosphazene-based epoxy resin (25g) and phosphazene-based resin curing agent (12g) prepared above were mixed and cured at 60°C for 2h, 100°C for 2h, 150°C for 3h, and 180°C for 1h to obtain an aging-resistant fluorinated epoxy resin.

[0222] Example 8

[0223] I. This embodiment provides a phosphazene-based epoxy resin:

[0224] Step A1: Hexachlorocyclotriphosphazene (1 mol), heptafluoropentanol (4 mol), terpineol (3 mol), and metallic sodium (7 mol) were added to DMA (2500 mL). The mixture was reacted at -18 °C for 3 h, then heated to 85 °C and reacted for 7 h. After the reaction was completed, the mixture was cooled to 20 °C, and the reaction solution was added to ethanol (8000 mL). The precipitate was dried to obtain a liquid intermediate product with the following structural formula:

[0225]

[0226] n is an integer from 1 to 6;

[0227] Step A2: Add the prepared liquid intermediate (1 mol) and hydrogen peroxide (5 mol) to DMA (1800 mL), heat to 50 °C and react for 9 h. After the reaction is complete, cool to room temperature, filter, evaporate and concentrate the filtrate, filter again, and dry the filtrate to obtain phosphazene-based epoxy resin with the following structural formula:

[0228]

[0229] n is an integer from 1 to 6.

[0230] II. This embodiment provides a phosphazene-based resin curing agent:

[0231] Step B1: Add m-aminophenol (1 mol) and cinnarizine (2 mol) to DMF (800 mL), react at 60 °C for 4 h, cool to room temperature, add petroleum ether (5000 mL) to precipitate, and dry to obtain the first intermediate product, with the following structural formula:

[0232]

[0233] Step B2: Hexachlorocyclotriphosphazene (1 mol), heptafluoropentanol (5 mol), the first intermediate (2 mol), and metallic sodium (7 mol) were added to THF (2100 mL). The mixture was reacted at -20 °C for 5 h, then heated to 100 °C and reacted for 36 h. After the reaction was completed, the mixture was cooled to 20 °C, and the reaction solution was added to ethanol (18000 mL). The precipitate was dried to obtain the second intermediate, with the following structural formula:

[0234]

[0235] m is an integer from 1 to 6;

[0236] Step B3: Dissolve the second intermediate (100g) in DMA (900mL), add acetic acid to bring the solution pH to 6, react at 90℃ for 3h, add petroleum ether (6000mL) to precipitate, repeat the operation 5 times, dry the precipitate to obtain the phosphazene-based resin curing agent, with the following structural formula:

[0237]

[0238] m is an integer from 1 to 6.

[0239] III. This embodiment provides an aging-resistant fluorinated epoxy resin:

[0240] The phosphazene-based epoxy resin (30g) and phosphazene-based resin curing agent (15g) prepared above were mixed and cured at 70°C for 2h, 110°C for 3h, 160°C for 2h, and 180°C for 1h to obtain an aging-resistant fluorinated epoxy resin.

[0241] Example 9

[0242] I. This embodiment provides a phosphazene-based epoxy resin:

[0243] Step A1: Hexachlorocyclotriphosphazene (1 mol) was added to DMA (2500 mL) along with p-trifluoromethylphenol (4 mol), 2-methyl-3-buten-2-ol (3 mol), and metallic sodium (7 mol). The mixture was reacted at -18 °C for 3 h, then heated to 85 °C and reacted for 7 h. After the reaction was completed, the mixture was cooled to 20 °C, and the reaction solution was added to ethanol (8000 mL). The precipitate was dried to obtain a liquid intermediate product with the following structural formula:

[0244]

[0245] n is an integer from 1 to 6;

[0246] Step A2: Add the prepared liquid intermediate (1 mol) and hydrogen peroxide (5 mol) to DMA (1800 mL), heat to 50 °C and react for 9 h. After the reaction is complete, cool to room temperature, filter, evaporate and concentrate the filtrate, filter again, and dry the filtrate to obtain phosphazene-based epoxy resin with the following structural formula:

[0247]

[0248] n is an integer from 1 to 6.

[0249] II. This embodiment provides a phosphazene-based resin curing agent:

[0250] Step B1: Isopropanolamine (1 mol) and benzaldehyde (2 mol) were added to DMF (800 mL), reacted at 60 °C for 4 h, cooled to room temperature, and then petroleum ether (5000 mL) was added to precipitate the product. After drying, the first intermediate product was obtained, with the following structural formula:

[0251]

[0252] Step B2: Hexachlorocyclotriphosphazene (1 mol), p-trifluoromethylphenol (5 mol), the first intermediate (2 mol), and metallic sodium (7 mol) were added to THF (2100 mL). The mixture was reacted at -20 °C for 5 h, then heated to 100 °C and reacted for 36 h. After the reaction was completed, the mixture was cooled to 20 °C, and the reaction solution was added to ethanol (18000 mL). The precipitate was dried to obtain the second intermediate, with the following structural formula:

[0253]

[0254] m is an integer from 1 to 6;

[0255] Step B3: Dissolve the second intermediate (100g) in DMA (900mL), add acetic acid to bring the solution pH to 6, react at 90℃ for 3h, add petroleum ether (6000mL) to precipitate, repeat the operation 5 times, dry the precipitate to obtain the phosphazene-based resin curing agent, with the following structural formula:

[0256]

[0257] m is an integer from 1 to 6.

[0258] III. This embodiment provides an aging-resistant fluorinated epoxy resin:

[0259] The phosphazene-based epoxy resin (30g) and phosphazene-based resin curing agent (12g) prepared above were mixed and cured at 60°C for 2h, 110°C for 3h, 150°C for 2h, and 180°C for 1h to obtain an aging-resistant fluorinated epoxy resin.

[0260] Comparative Example 1

[0261] This comparative example provides an epoxy resin, prepared by the following method:

[0262] Step a, preparing phosphazene-based epoxy resin, is exactly the same as in Example 7, and will not be repeated here;

[0263] Step b: The prepared phosphazene-based epoxy resin (25g) and 4,4'-diaminodiphenylmethane (6g) were cured at 80°C for 2h, at 100°C for 2h, at 150°C for 3h, and at 180°C for 1h to obtain epoxy resin.

[0264] Comparative Example 2

[0265] This comparative example provides an epoxy resin, prepared by the following method:

[0266] Step a, preparing the phosphazene-based resin curing agent, is exactly the same as in Example 3, and will not be repeated here;

[0267] Step b: 25g of epoxy resin (E-44) and 15g of the phosphazene-based resin curing agent prepared above are cured at 80°C for 2 hours, 110°C for 2 hours, 160°C for 3 hours, and 190°C for 1 hour to obtain epoxy resin.

[0268] Comparative Example 3

[0269] This comparative example provides an epoxy resin, prepared by the following method:

[0270] Step A1: 1 mol of hexachlorocyclotriphosphazene, 4 mol of n-pentanol, 3 mol of terpineol, and 7 mol of metallic sodium were added to DMA (2500 mL). The mixture was reacted at -18 °C for 3 h, then heated to 85 °C and reacted for 7 h. After the reaction was complete, the mixture was cooled to 20 °C, and the reaction solution was added to 8000 mL of ethanol. The precipitate was dried to obtain a fluorine-free liquid intermediate with the following structural formula:

[0271]

[0272] n is an integer from 1 to 6;

[0273] Step A2: Add 1 mol of the fluorine-free liquid intermediate and 5 mol of hydrogen peroxide to DMA (1800 ml), heat to 50°C and react for 9 hours. After the reaction is complete, cool to room temperature, filter, evaporate and concentrate the filtrate, filter again, and dry the filtrate to obtain a fluorine-free phosphazene-based epoxy resin with the following structural formula:

[0274]

[0275] n is an integer from 1 to 6;

[0276] Step B1: Add m-aminophenol (1 mol) and cinnarizine (2 mol) to DMF (800 mL), react at 60 °C for 4 h, cool to room temperature, add petroleum ether (5000 mL) to precipitate, and dry to obtain the first intermediate product, with the following structural formula:

[0277]

[0278] Step B2: Hexachlorocyclotriphosphazene (1 mol), n-pentanol (5 mol), the first intermediate (2 mol), and metallic sodium (7 mol) were added to THF (2100 mL). The mixture was reacted at -20 °C for 5 h, then heated to 100 °C and reacted for 36 h. After the reaction was completed, the mixture was cooled to 20 °C, and the reaction solution was added to ethanol (18000 mL). The precipitate was dried to obtain a fluorine-free second intermediate with the following structural formula:

[0279]

[0280] m is an integer from 1 to 6;

[0281] Step B3: Dissolve the second intermediate (100g) in DMA (900mL), add acetic acid to bring the solution pH to 6, react at 90℃ for 3h, add petroleum ether (6000ml) to precipitate, repeat the operation 5 times, dry the precipitate to obtain a fluorophosphazene-based resin curing agent with the following structural formula:

[0282]

[0283] m is an integer from 1 to 6;

[0284] Step C: Mix 25g of fluorophosphazene-based epoxy resin and 15g of fluorophosphazene-based resin curing agent, cure at 70°C for 2 hours, at 110°C for 3 hours, at 160°C for 2 hours, and at 180°C for 1 hour to obtain epoxy resin.

[0285] Performance testing

[0286] The tensile strength test standard for the epoxy resin samples prepared in the embodiments and comparative examples of this invention is GB / T1040.2-2022, using type 1BA specimens; the limiting oxygen index test standard is GB / T 2406.2-2009, using type I specimens; the vertical burning test standard is GB / T 2406.2-2009, with a specimen thickness of 3.2±0.25mm; the residue test standard at 700℃ is GB / T 27761-2011; the glass transition temperature test standard is GB / T 19466.2-2004; the heat aging test method is Method B in GB / T 7141-2008, with an exposure temperature of 110℃ and an exposure period of 24 hours. The tensile strength of the heat-aged specimens was tested according to GB / T 1040.2-2022, using type 1BA specimens. The results are shown in Table 1.

[0287] Table 1

[0288]

[0289]

[0290] The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention. Any modifications, equivalent substitutions or improvements made within the spirit and principles of the present invention should be included within the protection scope of the present invention.

Claims

1. A phosphazene-based resin curing agent, characterized in that, Its structural formula is shown in equation (Ⅰ): Where m is an integer from 1 to 6; R2 is selected from C2 to C10 fluorinated alkyl groups, fluorinated phenyl groups, or fluorinated alkylphenyl groups; wherein the fluorinated alkyl group contains two or more fluorine atoms; R4 is selected from phenyl, nitrophenyl, cyclohexyl, adamantyl, or C2-C5 alkyl groups.

2. The phosphazene-based resin curing agent as described in claim 1, characterized in that, R2 is selected from the following groups:

3. The phosphazene-based resin curing agent as described in claim 1, characterized in that, R4 is selected from the following groups: In this context, * indicates the position where the group is attached to the N atom.

4. The method for preparing the phosphazene-based resin curing agent according to any one of claims 1 to 3, characterized in that, Includes the following steps: S1, condensation reaction of aminophenol / alcohol compound NH2-R4-OH and aldehyde substance R3-CHO to obtain intermediate 1 as shown in formula (II); S2, under acid-binding conditions, hexachlorocyclophosphamide, fluorophenol / alcohol compound R2-OH and intermediate 1 undergo a substitution reaction to obtain intermediate 2 as shown in formula (Ⅲ); S3, the intermediate 2 is hydrolyzed under acidic conditions to obtain the phosphazene-based resin curing agent shown in formula (Ⅰ).

5. The method for preparing the phosphazene-based resin curing agent as described in claim 1, characterized in that, In S1, the aminophenol / alcohol compound is at least one of p-aminophenol, m-aminophenol, o-aminophenol, 2-amino-4-nitrophenol, 2-aminocyclohexanol, 3-aminoadamantanol, or isopropanolamine; and / or In S1, the aldehyde is at least one of formaldehyde, acetaldehyde, furfural, decanal, n-butyraldehyde, n-propionaldehyde, benzaldehyde, undecylaldehyde, dodecanaldehyde, pentadecylaldehyde, theobromaldehyde, isobutyraldehyde, isovaleraldehyde, cinnamaldehyde, or cinnamaldehyde; and / or In S2, the fluoroethanol / phenol compound includes at least one of difluoroethanol, trifluoroethanol, tetrafluoropropanol, pentafluoropropanol, hexafluoroisopropanol, hexafluorobutanol, heptafluorobutanol, heptafluoropentanol, octafluoropentanol, nonafluoropentanol, nonafluorohexanol, dodecafluoroheptanol, p-trifluoromethylphenol, m-trifluoromethylphenol, o-trifluoromethylphenol, 4-ethyl-2,6-difluorophenol, 2-ethyl-4-fluorophenol, 3-ethyl-4-fluorophenol, 4-fluorophenol, and 2-fluorophenol; and / or In S2, the acid-binding agent is at least one of calcium carbonate, potassium carbonate, cesium carbonate, triethylamine, sodium metal, sodium hydride, or potassium metal.

6. A method for preparing a phosphazene-based epoxy resin, characterized in that, Includes the following steps: Step a: Under acid-binding conditions, hexachlorocyclotriphosphazene, double-bonded alcohol / phenol compound R1-OH and fluorinated alcohol / phenol compound R2-OH react to obtain intermediate a shown in (Ⅳ); Step b: The intermediate a is added to an oxidant solution to carry out an oxidation reaction, thereby obtaining a phosphazene-based epoxy resin.

7. The method for preparing the phosphazene-based epoxy resin as described in claim 6, characterized in that, In step a, the double-bonded alcohol / phenol compound includes at least one of ethylene glycol monovinyl ether, 2-methyl-3-buten-2-ol, eugenol, cashew nut shell powder, 4-allylphenol, or terpineol; and / or In step a, the fluoroethanol / phenol compound includes at least one of difluoroethanol, trifluoroethanol, tetrafluoropropanol, pentafluoropropanol, hexafluoroisopropanol, hexafluorobutanol, heptafluorobutanol, heptafluoropentanol, octafluoropentanol, nonafluoropentanol, nonafluorohexanol, dodecafluoroheptanol, p-trifluoromethylphenol, m-trifluoromethylphenol, o-trifluoromethylphenol, 4-ethyl-2,6-difluorophenol, 2-ethyl-4-fluorophenol, 3-ethyl-4-fluorophenol, 4-fluorophenol, or 2-fluorophenol; and / or In step a, the acid-binding agent is at least one selected from calcium carbonate, potassium carbonate, cesium carbonate, triethylamine, sodium metal, sodium hydride, or potassium metal; and / or In step b, the oxidant in the oxidant solution is selected from one or more of m-chloroperoxybenzoic acid, hydrogen peroxide, peracetic acid, peroxybenzoic acid, tert-butanol hydroperoxide, or cumene hydroperoxide; the solvent is selected from one or more of dimethylformamide, dimethylacetamide, tetrahydrofuran, dimethyl sulfoxide, dichloromethane, or chloroform.

8. A phosphazene-based epoxy resin, characterized in that, It is prepared by the method for preparing phosphazene-based epoxy resin according to claim 6 or 7.

9. An aging-resistant fluorinated epoxy resin, characterized in that, It is prepared by curing the phosphazene-based epoxy resin according to claim 8 and the phosphazene-based resin curing agent according to any one of claims 1 to 3.

10. The application of the aging-resistant fluorinated epoxy resin according to claim 9 in the field of electronic packaging materials.

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