Preparation method of high-performance phosphorus-containing self-repairing epoxy resin

Abstract

The invention relates to the technical field of self-repairing epoxy resin, in particular to a preparation method of high-performance phosphorus-containing self-repairing epoxy resin, which comprises the following steps: firstly, preparing an intermediate containing a network structure with flexible dynamic points and rigid crosslinking points, constructing double dynamic bonds, reacting to obtain ester groups and amino hydroxyl groups to construct a rigid crosslinking skeleton, and preparing the high-performance phosphorus-containing self-repairing epoxy resin. The disilane modified silicon dioxide particles have self-repairing and mechanical properties in cooperation with hard sites of the nanoparticles, and then have a cross-linking reaction with a phosphorus-containing compound monomer, phosphorus atoms and hydroxyl groups of an intermediate form phosphorus-oxygen bonds (having flame-retardant and cross-linking effects), and the disilane modified silicon dioxide particles can be combined with hydrogen bonds of the intermediate and the phosphorus-containing compound monomer and promote generation of dynamic bonds. The prepared epoxy resin has multiple self-repairing functions, can be sustainably utilized, and also has good mechanical properties and flame retardant properties; the invention effectively solves the joint debugging contradiction between the self-repairing performance and the thermal mechanical performance of the traditional epoxy resin, and can be applied to the fields of high frequency, high density, microelectronics and the like.

Description

Technical Field

[0001] This invention relates to the field of self-healing epoxy resin technology, specifically to a method for preparing a high-performance phosphorus-containing self-healing epoxy resin. Background Technology

[0002] Epoxy resins are widely used in coatings, adhesives, electronic packaging, aerospace, and composite matrix applications due to their excellent mechanical strength, good chemical resistance, high bond strength, low shrinkage, and good dimensional stability. The most crucial characteristic of phosphorus-containing epoxy resins is their inherent flame-retardant properties; they are halogen-free and environmentally friendly materials with excellent performance. However, traditional epoxy resins form a highly cross-linked three-dimensional network structure after curing, making them hard but also often brittle. Under external impact or stress, they are prone to microcracks, severely affecting the structural integrity and service life of the material. Therefore, improving the toughness of epoxy resins and endowing them with self-healing capabilities is of significant research value and practical importance for extending material service life and improving structural reliability. Currently, research on achieving self-healing functionality in epoxy resins mainly falls into two strategies: extrinsic and intrinsic. Intrinsic self-healing involves introducing dynamic chemical bonds or supramolecular interactions into the epoxy resin network, enabling the broken chemical bonds to reform under external stimuli, thereby achieving autonomous crack healing. Although intrinsic self-healing shows the potential for repeated repair, existing technologies often face the following challenges: the introduction of dynamic bonds may weaken the original high modulus and high strength of the material, and the repair process requires high temperatures or long repair times.

[0003] Therefore, a technology is needed that can retain the excellent mechanical properties of liquid crystal epoxy resin, while also achieving the self-healing and environmentally friendly properties of the material, providing a new solution for the sustainable development of fields such as electronic packaging, aerospace, and energy equipment. Summary of the Invention

[0004] The technical problem to be solved by the present invention is to provide a method for preparing and recycling high-performance phosphorus-containing self-healing epoxy resin, so as to solve the problem that the mechanical properties, flame retardant properties and recyclability of epoxy resin in the prior art cannot be achieved at the same time.

[0005] This invention solves the above-mentioned technical problems. The invention provides a method for preparing a high-performance phosphorus-containing self-healing epoxy resin, comprising the following steps: Step 1: Modify nano-SiO2 with a silane reactant to obtain nanoparticles: The modification process involves ultrasonically dispersing nano-SiO2 in anhydrous ethanol containing 0.2-0.3 wt% PEG-PPG at an ultrasonic frequency of 18-22 kHz for 20-30 min to form a suspension. A silane reactant of 10-14 wt% nano-SiO2 is then added dropwise to the suspension, and the mixture is stirred at 50-60°C for 80-100 min. After centrifugation, washing, and spray drying, nanoparticles are obtained. Amino and phenolic hydroxyl groups are introduced onto the SiO2 surface through silane hydrolysis and condensation reactions, enabling the formation of Diels-Alder bonds and hydrogen bonds with the furfuryl ether ring of the intermediate, while simultaneously providing hard sites to the resin and improving its mechanical properties. The silane reactants are p-hydroxyphenylpropyltrimethoxysilane and 3-aminopropyltriethoxysilane in a mass ratio of 4-6:2-4; Step 2: Preparation of intermediates; Under nitrogen protection, glycidyl furfuryl ether and amino polyacid are added to a reaction vessel at a molar ratio of 3-4:1, and the mixture is heated to 100-105℃ and reacted for 1-2.5 h; the mixture is cooled to 75-85℃, 8-10 wt% of composite toughening agent and 0.5-0.8 wt% of solid catalyst SO4²⁻ / ZrO2 are added, and the mixture is stirred for 1-3 h; then 6-10 wt% of polyhydroxy polyol, 3-5 wt% of dimercaptosuccinic acid and 4-6 wt% of the nanoparticles prepared in step 1 are added, and the mixture is stirred for 4-6 h to obtain the final product; The amino polyacid is one of aminoadipic acid and aminopimepic acid; The composite toughening agent is polycaprolactone and adipic acid in a mass ratio of 2:0.4-0.8; The solid catalyst has a particle size of 50-100 nm and is activated by calcination at 450 °C. The polyhydroxy polyol is one of pentaerythritol and trimethylolpropane; The epoxy group undergoes a ring-opening reaction with the amino polyacid to generate hydroxyl and aminohydroxyl structures, which enhances the binding ability with phosphorus-containing monomers. It also generates olefin double bonds containing α,β-unsaturated lactone structures by controlling the selective hydrolysis-intramolecular cyclization reaction of polycaprolactone. The surface active groups of nanoparticles catalyze the condensation reaction of disulfide bonds, while promoting the formation of Diels-Alder dynamic bonds between α,β-unsaturated lactone and furfural ring. Step 3: React the phosphorus-containing monomer, intermediate and solvent at 60-70℃ for 4-6 h. After the reaction is complete, filter, collect the filtrate and remove the solvent by vacuum distillation. The obtained solid is recrystallized from ethanol and dried to obtain product P1. The phosphorus-containing monomer is one of dichlorophosphine, hexachlorotriphosphazene, and phosphoryl chloride, and the mass ratio of the phosphorus-containing monomer, intermediate, and solvent is 1.0:(2-6.2):10; The solvent is one of ethyl lactate, γ-valerolactone, ethanol, and ethyl acetate; Step 4: Product P1 is mixed with an equal amount of epichlorohydrin, and 0.5 wt% tetrabutylammonium bromide catalyst is added. The mixture is stirred at 60-80℃ for 8-12 h. After the reaction is completed, epoxy resin P2 is obtained by vacuum distillation. Step 5: Mix epoxy resin P2 with bisphenol A epoxy resin and aliphatic amine curing agent at a mass ratio of 10-25:75-100:28-31, cure at 80-120℃ for 2-4 h, and then cool naturally to obtain high-performance phosphorus-containing self-healing epoxy resin. The fatty amine curing agent is one of diethylenetriamine, triethylenetetramine, and D230.

[0006] The beneficial effects of this invention are as follows: The present invention provides a method for preparing high-performance phosphorus-containing self-healing epoxy resin. First, an intermediate containing a network structure with both flexible dynamic points and rigid cross-linking points is prepared. A rigid cross-linking framework is constructed by building dual dynamic bonds: amino polyacids ring-opening with glycidyl furfuryl ether to form amino hydrocarbon groups, and polyhydroxy polyols forming ester and amide bonds. Combined with the hard sites of nanoparticles, it possesses both self-healing and mechanical properties. Then, it undergoes a cross-linking reaction with a phosphorus-containing compound monomer. Phosphorus atoms form phosphorus-oxygen bonds with the hydroxyl groups of the intermediate (providing both flame retardancy and cross-linking effects). The bissilane-modified silica microparticles can interact with the intermediate... The intermediate and phosphorus-containing monomers are hydrogen-bonded and promote the formation of Diels-Alder dynamic bonds and disulfide bonds. The disulfide bonds repair microcracks at room temperature, while the Diels-Alder dynamic bonds repair large cracks at high temperature, giving epoxy resin multiple self-healing functions and enabling the sustainable use of epoxy resin. At the same time, it has excellent mechanical properties, with a tensile strength of 103 MPa, a flexural strength of 148 MPa, and an impact strength of 41.4 MPa. It also has good flame retardant properties, with an oxygen index of 42%, and the repair rate of epoxy resin after heat repair is high.

[0007] The high-performance phosphorus-containing self-healing epoxy resin prepared by this invention has mechanical properties, flame retardant properties and self-healing properties, and can be used in electronic packaging, aerospace, energy equipment and other fields. Detailed Implementation

[0008] The present invention will be further described in detail below through specific implementation examples. It should be understood that these embodiments are only used to illustrate the present invention and are not intended to limit the scope of protection of the present invention. After reading the present invention, any modifications of the present invention in various equivalent forms by those skilled in the art fall within the scope of the appended claims.

[0009] Unless otherwise specified, all raw materials and reagents used in this invention are from the conventional market.

[0010] Example 1 A method for preparing a high-performance phosphorus-containing self-healing epoxy resin includes the following steps: Step 1: Preparation of nanoparticles: Nano-SiO2 was ultrasonically dispersed in anhydrous ethanol containing 0.2wt% PEG-PPG at an ultrasonic frequency of 20kHz for 25min to form a suspension. Silane reactant of 12wt% of nano-SiO2 was added dropwise to the suspension, and the mixture was stirred at 55℃ for 90min. After centrifugation, washing, and spray drying, nanoparticles were obtained. The silane reactants are p-hydroxyphenylpropyltrimethoxysilane and 3-aminopropyltriethoxysilane in a mass ratio of 5:3; Step 2: Preparation of intermediates; Under nitrogen protection, glycidyl furfuryl ether and aminoadipic acid were added to a reaction vessel at a molar ratio of 3:1, and the mixture was heated to 100℃ and reacted for 2 hours; the mixture was cooled to 80℃, and 9 wt% of composite toughening agent and 0.7 wt% of solid catalyst SO4²⁻ / ZrO2 were added, and the mixture was stirred and reacted for 2 hours. Then, 8 wt% of trimethylolpropane, 4 wt% of dimercaptosuccinic acid and 5 wt% of the nanoparticles prepared in Step 1 were added, and the mixture was stirred and reacted for 5 hours to obtain the final product. The composite toughening agent contains polycaprolactone and adipic acid in a mass ratio of 2:0.4-0.8; The solid catalyst has a particle size of 50-100 nm and is activated by calcination at 450 °C. Step 3: The dichlorophosphine, intermediate and ethyl lactate in a mass ratio of 1.0:4:10 were reacted at 65°C for 5 h. After the reaction was completed, the mixture was filtered, the filtrate was collected and the solvent was removed by vacuum distillation. The obtained solid was recrystallized from ethanol and dried to obtain product P1. Step 4: Product P1 is mixed with an equal amount of epichlorohydrin, and 0.5 wt% tetrabutylammonium bromide catalyst is added. The mixture is stirred at 70 °C for 10 h. After the reaction is completed, epoxy resin P2 is obtained by vacuum distillation. Step 5: Mix epoxy resin P2 with bisphenol A epoxy resin and D230 at a mass ratio of 20:90:30, cure at 100℃ for 3 h, and then allow to cool naturally to obtain a high-performance phosphorus-containing self-healing epoxy resin.

[0011] Cut a 70% height notch in the cured phosphorus-containing self-healing epoxy resin sample and heat it at 120℃ for 2 hours to obtain the repaired epoxy resin.

[0012] Example 2 A method for preparing a high-performance phosphorus-containing self-healing epoxy resin includes the following steps: Step 1: Preparation of nanoparticles: Nano-SiO2 was ultrasonically dispersed in anhydrous ethanol containing 0.2wt% PEG-PPG at an ultrasonic frequency of 18kHz for 20min to form a suspension. Silane reactant of 10wt% nano-SiO2 was added dropwise to the suspension, and the mixture was stirred at 50℃ for 80min. After centrifugation, washing, and spray drying, nanoparticles were obtained. The silane reactants are p-hydroxyphenylpropyltrimethoxysilane and 3-aminopropyltriethoxysilane in a mass ratio of 4:2; Step 2: Preparation of intermediates; Under nitrogen protection, glycidyl furfuryl ether and aminopimelic acid were added to a reaction vessel at a molar ratio of 3:1, and the mixture was heated to 100℃ and reacted for 1 hour; the mixture was cooled to 75℃, and 8 wt% of composite toughening agent and 0.5 wt% of solid catalyst SO4²⁻ / ZrO2 were added, and the mixture was stirred and reacted for 1 hour. Then, 6 wt% of trimethylolpropane, 3 wt% of dimercaptosuccinic acid and 4 wt% of the nanoparticles prepared in Step 1 were added, and the mixture was stirred and reacted for 4 hours to obtain the final product. The composite toughening agent contains polycaprolactone and adipic acid in a mass ratio of 2:0.4; The solid catalyst has a particle size of 50 nm and is activated by calcination at 450 °C. Step 3: Hexachlorotriphosphazene, intermediate and γ-valerol were reacted at 60℃ for 4 h in a mass ratio of 1.0:2:10. After the reaction was completed, the mixture was filtered, the filtrate was collected and the solvent was removed by vacuum distillation. The obtained solid was recrystallized from ethanol and dried to obtain product P1. Step 4: Product P1 is mixed with an equal amount of epichlorohydrin, and 0.5 wt% tetrabutylammonium bromide catalyst is added. The mixture is stirred at 60 °C for 8 h. After the reaction is completed, epoxy resin P2 is obtained by vacuum distillation. Step 5: Mix epoxy resin P2 with bisphenol A epoxy resin and triethylenetetramine in a mass ratio of 10:75:28, cure at 80°C for 2 hours, and then allow to cool naturally to obtain a high-performance phosphorus-containing self-healing epoxy resin.

[0013] Cut a 70% height notch in the cured phosphorus-containing self-healing epoxy resin sample and heat it at 120℃ for 2 hours to obtain the repaired epoxy resin.

[0014] Example 3 A method for preparing a high-performance phosphorus-containing self-healing epoxy resin includes the following steps: Step 1: Preparation of nanoparticles: Nano-SiO2 was ultrasonically dispersed in anhydrous ethanol containing 0.3wt% PEG-PPG at an ultrasonic frequency of 22kHz for 30min to form a suspension. Silane reactant of 14wt% nano-SiO2 was added dropwise to the suspension, and the mixture was stirred at 60℃ for 100min. After centrifugation, washing, and spray drying, nanoparticles were obtained. The silane reactants are p-hydroxyphenylpropyltrimethoxysilane and 3-aminopropyltriethoxysilane in a mass ratio of 6:4. Step 2: Preparation of intermediates; Under nitrogen protection, glycidyl furfuryl ether and aminopimelic acid were added to a reaction vessel at a molar ratio of 4:1, and the mixture was heated to 105℃ and reacted for 2.5 h; the temperature was lowered to 85℃, 10 wt% of composite toughening agent and 0.8 wt% of solid catalyst SO4²⁻ / ZrO2 were added, and the mixture was stirred and reacted for 3 h; then 10 wt% of pentaerythritol, 5 wt% of dimercaptosuccinic acid and 6 wt% of the nanoparticles prepared in step 1 were added, and the mixture was stirred and reacted for 6 h to obtain the final product; The composite toughening agent contains polycaprolactone and adipic acid in a mass ratio of 2:0.8; The solid catalyst has a particle size of 50-100 nm and is activated by calcination at 450 °C. Step 3: Phosphoryl chloride, intermediate and ethanol in a mass ratio of 1.0:6.2:10 were reacted at 70℃ for 6 h. After the reaction was completed, the mixture was filtered, the filtrate was collected and the solvent was removed by vacuum distillation. The obtained solid was recrystallized from ethanol and dried to obtain product P1. Step 4: Product P1 is mixed with an equal amount of epichlorohydrin, and 0.5 wt% tetrabutylammonium bromide catalyst is added. The mixture is stirred at 80 °C for 12 h. After the reaction is completed, epoxy resin P2 is obtained by vacuum distillation. Step 5: Mix epoxy resin P2 with bisphenol A epoxy resin and triethylenetetramine at a mass ratio of 25:100:31, cure at 120℃ for 4 h, and then allow to cool naturally to obtain a high-performance phosphorus-containing self-healing epoxy resin.

[0015] Cut a 70% height notch in the cured phosphorus-containing self-healing epoxy resin sample and heat it at 120℃ for 2 hours to obtain the repaired epoxy resin.

[0016] Example 4 A method for preparing a high-performance phosphorus-containing self-healing epoxy resin includes the following steps: Step 1: Preparation of nanoparticles: Nano-SiO2 was ultrasonically dispersed in anhydrous ethanol containing 0.2wt% PEG-PPG at an ultrasonic frequency of 22kHz for 20min to form a suspension. Silane reactant of 11wt% of nano-SiO2 was added dropwise to the suspension, and the mixture was stirred at 50-60℃ for 90min. After centrifugation, washing, and spray drying, nanoparticles were obtained. The silane reactants are p-hydroxyphenylpropyltrimethoxysilane and 3-aminopropyltriethoxysilane in a mass ratio of 4:3; Step 2: Preparation of intermediates; Under nitrogen protection, glycidyl furfuryl ether and aminoadipic acid were added to a reaction vessel at a molar ratio of 3:1, and the mixture was heated to 105℃ and reacted for 1 h; the mixture was cooled to 85℃, and 8 wt% of composite toughening agent and 0.6 wt% of solid catalyst SO4²⁻ / ZrO2 were added, and the mixture was stirred and reacted for 1 h. Then, 7 wt% of trimethylolpropane, 3 wt% of dimercaptosuccinic acid and 4 wt% of the nanoparticles prepared in Step 1 were added, and the mixture was stirred and reacted for 4 h to obtain the final product; The composite toughening agent contains polycaprolactone and adipic acid in a mass ratio of 2:0.5; The solid catalyst has a particle size of 50-100 nm and is activated by calcination at 450 °C. Step 3: Dichlorophosphine, intermediate and ethyl acetate in a mass ratio of 1.0:3:10 were reacted at 60℃ for 6 h. After the reaction was completed, the mixture was filtered, the filtrate was collected and the solvent was removed by vacuum distillation. The obtained solid was recrystallized from ethanol and dried to obtain product P1. Step 4: Product P1 is mixed with an equal amount of epichlorohydrin, and 0.5 wt% tetrabutylammonium bromide catalyst is added. The mixture is stirred at 60°C for 9 h. After the reaction is completed, epoxy resin P2 is obtained by vacuum distillation. Step 5: Mix epoxy resin P2 with bisphenol A epoxy resin and D230 at a mass ratio of 12:80:28, cure at 90℃ for 2 hours, and then allow to cool naturally to obtain a high-performance phosphorus-containing self-healing epoxy resin.

[0017] Cut a 70% height notch in the cured phosphorus-containing self-healing epoxy resin sample and heat it at 120℃ for 2 hours to obtain the repaired epoxy resin.

[0018] Example 5 A method for preparing a high-performance phosphorus-containing self-healing epoxy resin includes the following steps: Step 1: Preparation of nanoparticles: Nano-SiO2 was ultrasonically dispersed in anhydrous ethanol containing 0.3wt% PEG-PPG at an ultrasonic frequency of 18kHz for 25min to form a suspension. Silane reactant of 13wt% nano-SiO2 was added dropwise to the suspension, and the mixture was stirred at 60℃ for 90min. After centrifugation, washing, and spray drying, nanoparticles were obtained. The silane reactants are p-hydroxyphenylpropyltrimethoxysilane and 3-aminopropyltriethoxysilane in a mass ratio of 5:4. Step 2: Preparation of intermediates; Under nitrogen protection, glycidyl furfuryl ether and aminoadipic acid were added to a reaction vessel at a molar ratio of 4:1, and the mixture was heated to 105℃ and reacted for 1 h; the mixture was cooled to 75℃, and 9 wt% of composite toughening agent and 0.7 wt% of solid catalyst SO4²⁻ / ZrO2 were added, and the mixture was stirred and reacted for 1 h. Then, 9 wt% of trimethylolpropane, 4 wt% of dimercaptosuccinic acid and 5 wt% of the nanoparticles prepared in Step 1 were added, and the mixture was stirred and reacted for 5 h to obtain the final product. The composite toughening agent contains polycaprolactone and adipic acid in a mass ratio of 2:0.4-0.8; The solid catalyst has a particle size of 50-100 nm and is activated by calcination at 450 °C. Step 3: Hexachlorotriphosphazene, intermediate and ethanol in a mass ratio of 1.0:5:10 were reacted at 70°C for 4 h. After the reaction was completed, the mixture was filtered, the filtrate was collected and the solvent was removed by vacuum distillation. The obtained solid was recrystallized from ethanol and dried to obtain product P1. Step 4: Product P1 is mixed with an equal amount of epichlorohydrin, and 0.5 wt% tetrabutylammonium bromide catalyst is added. The mixture is stirred at 70 °C for 11 h. After the reaction is completed, epoxy resin P2 is obtained by vacuum distillation. Step 5: Mix epoxy resin P2 with bisphenol A epoxy resin and diethylenetriamine in a mass ratio of 22:95:30, cure at 90°C for 2 hours, and then allow to cool naturally to obtain a high-performance phosphorus-containing self-healing epoxy resin.

[0019] Cut a 70% height notch in the cured phosphorus-containing self-healing epoxy resin sample and heat it at 120℃ for 2 hours to obtain the repaired epoxy resin.

[0020] Comparative Example 1 The difference between Comparative Example 1 and Example 2 is that Comparative Example 1 does not add amino polyacids, while everything else remains the same.

[0021] Comparative Example 2 The difference between Comparative Example 2 and Example 2 is that Comparative Example 2 does not add polyhydroxy polyols, while everything else remains the same.

[0022] Comparative Example 3 The difference between Comparative Example 3 and Example 2 is that Comparative Example 3 uses an equal amount of polycaprolactone instead of the composite toughening agent, while everything else remains the same.

[0023] Comparative Example 4 The difference between Comparative Example 4 and Example 2 is that Comparative Example 4 uses an equal amount of nano-silica instead of nanoparticles, while everything else remains the same.

[0024] I. The epoxy resin cured products prepared in Examples 1-5 and Comparative Examples 1-4 were placed at 25°C for 24 h and their tensile properties were determined according to ASTM 3039. The flexural strength, impact strength, and oxygen index of the epoxy resin cured products were tested according to ASTM D790, ASTM D256, and ASTM D2863, respectively (sample size: 100mm × 6.5mm × 3mm). The self-healing performance of the self-healing epoxy resin was further tested after self-healing treatment at 120°C under no-pressure conditions for 2 h. The repair rate was calculated by comparing the detected data with the data detected before self-healing. The specific results are shown in Table 1.

[0025] Table 1 Mechanical properties and flame retardant properties of Examples 1-5 and Comparative Examples 1-4 As shown in Table 1, the epoxy resin prepared by this invention has good mechanical properties, including good tensile strength, flexural strength and impact strength, and has a high oxygen index, good flame retardant properties and self-healing properties. As can be seen from Comparative Example 1, the intermediate prepared by the present invention adds amino polyacids, which form active groups such as amino hydroxyl groups through ring-opening reactions, protect and promote the generation of dynamic bonds, and play a toughening role through reactions such as esterification. As can be seen from Comparative Example 2, the intermediate prepared by the present invention introduces hydroxyl groups and other groups by adding polyhydroxyl polyols to react with phosphorus monomers to form phosphorus oxygen bonds, thereby improving flame retardancy and self-healing effects, while optimizing the spatial properties of epoxy resin and regulating the dynamic bond distribution. As can be seen from Comparative Example 3, the addition of composite toughening agent to the intermediate prepared by the present invention, compared with single polycaprolactone, adipic acid can increase the hydrolysis rate of polycaprolactone, promote the formation of Diels-Alder bonds, and improve the stability of disulfide bonds. It can also react with polyhydroxy polyols to form linear ester bonds, thereby improving the mechanical properties of epoxy resin and improving its self-healing properties. As shown in Comparative Example 4, nanoparticles, through dual modification with silane reactants, can promote the dispersion and compatibility of silica in resins, and promote the formation of dynamic bonds in intermediates through surface-active groups, thereby improving the self-healing and mechanical properties of epoxy resins.

Claims

1. A method for preparing a high-performance phosphorus-containing self-healing epoxy resin, characterized in that, Includes the following steps: Step 1: Modify nano-SiO2 with silane reactant to obtain nanoparticles; The silane reactants are p-hydroxyphenylpropyltrimethoxysilane and 3-aminopropyltriethoxysilane in a mass ratio of 4-6:2-4; Step 2: Preparation of intermediates: Under nitrogen protection, glycidyl furfuryl ether and amino polyacid are added to a reaction vessel at a molar ratio of 3-4:1, and the mixture is heated to 100-105℃ and reacted for 1-2.5 h; the mixture is then cooled to 75-85℃, and 8-10 wt% of composite toughening agent and 0.5-0.8 wt% of solid catalyst SO4²⁻ / ZrO2 are added. The mixture is stirred and reacted for 1-3 h, and then 6-10 wt% of polyhydroxy polyol, 3-5 wt% of dimercaptosuccinic acid and 4-6 wt% of the nanoparticles prepared in Step 1 are added. The mixture is stirred and reacted for 4-6 h to obtain the final product. The composite toughening agent is polycaprolactone and adipic acid in a mass ratio of 2:0.4-0.8; Step 3: React the phosphorus-containing monomer, intermediate and solvent at 60-70℃ for 4-6 h. After the reaction is complete, filter, collect the filtrate and remove the solvent by vacuum distillation. The obtained solid is recrystallized from ethanol and dried to obtain product P1. The phosphorus-containing monomer is one of dichlorophosphine, hexachlorotriphosphazene, and phosphoryl chloride, and the mass ratio of the phosphorus-containing monomer, intermediate, and solvent is 1.0:(2-6.2):10; Step 4: Product P1 is mixed with an equal amount of epichlorohydrin, and 0.5 wt% tetrabutylammonium bromide catalyst is added. The mixture is stirred at 60-80℃ for 8-12 h. After the reaction is completed, epoxy resin P2 is obtained by vacuum distillation. Step 5: Mix epoxy resin P2 with bisphenol A epoxy resin and aliphatic amine curing agent at a mass ratio of 10-25:75-100:28-31, cure at 80-120℃ for 2-4 hours, and then allow to cool naturally to obtain high-performance phosphorus-containing self-healing epoxy resin.

2. The method for preparing a high-performance phosphorus-containing self-healing epoxy resin according to claim 1, characterized in that, The modification process described in step 1 involves ultrasonically dispersing nano-SiO2 in anhydrous ethanol containing 0.2-0.3 wt% PEG-PPG at an ultrasonic frequency of 18-22 kHz for 20-30 min to form a suspension. A silane reactant of 10-14 wt% nano-SiO2 is then added dropwise to the suspension, and the mixture is stirred at 50-60℃ for 80-100 min. After centrifugation, washing, and spray drying, nanoparticles are obtained.

3. The method for preparing a high-performance phosphorus-containing self-healing epoxy resin according to claim 1, characterized in that, The amino polyacid mentioned in step 2 is one of aminoadipic acid or aminopimepic acid.

4. The method for preparing a high-performance phosphorus-containing self-healing epoxy resin according to claim 1, characterized in that, The solid catalyst in step 2 has a particle size of 50-100 nm and is activated by calcination at 450 °C.

5. The method for preparing a high-performance phosphorus-containing self-healing epoxy resin according to claim 1, characterized in that, The polyol mentioned in step 2 is one of pentaerythritol and trimethylolpropane.

6. The method for preparing a high-performance phosphorus-containing self-healing epoxy resin according to claim 1, characterized in that, The solvent mentioned in step 3 is one of ethyl lactate, γ-valerol, ethanol, and ethyl acetate.

7. The method for preparing a high-performance phosphorus-containing self-healing epoxy resin according to claim 1, characterized in that, The fatty amine curing agent mentioned in step 5 is one of diethylenetriamine, triethylenetetramine, and D230.

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