Flame-retardant high-modulus and high-toughness winding epoxy resin composition and preparation method thereof

Abstract

The invention relates to the field of epoxy resin, in particular to a flame-retardant high-modulus and high-toughness winding epoxy resin composition and a preparation method thereof.The epoxy resin composition comprises an epoxy resin component A and a curing agent component B; the epoxy resin component A comprises the following raw materials in parts by weight: 40-50 parts of an epoxy resin mixture, 35-45 parts of a flame retardant, 8-9 parts of a diluent, 6-15 parts of a flexibilizer and 0.5-1 part of a surfactant; wherein the flexibilizer is a mixture of shell-core rubber and CNTs (Carbon Nanotubes) in a weight part ratio of (5-15): (0.2-1). The problem that a traditional epoxy resin matrix material is insufficient in high strength, toughness and flame retardance is solved.

Description

Technical Field

[0001] The present application relates to the field of epoxy resins, and more specifically, to a flame retardant high modulus, high toughness winding epoxy resin composition and a preparation method thereof. Background Art

[0002] With the upgrading of modern military needs, traditional metal airborne equipment is difficult to meet the lightweight requirements due to its heavy weight, easy rust, process defects and other problems. Composite materials have shown significant potential in improving storage reliability, launch accuracy and battlefield adaptability by virtue of their advantages such as high specific strength, high specific modulus and designability, and have become the ideal material for the new generation of launch tubes. Resin-based composite materials with carbon fiber as reinforcement and epoxy resin as matrix have been widely used in the field of launch tube manufacturing due to their light weight, high strength, corrosion resistance and fatigue resistance.

[0003] In actual use, the launch tube needs to maintain launch accuracy and stability under the challenges of extreme temperature, launch shock and other conditions; this requires its molding material to take into account good mechanical stability and certain fire protection requirements to ensure the battlefield adaptability and full life cycle reliability of the launch tube. Traditional epoxy resin products have problems such as low strength and poor toughness, and do not have flame retardant properties and cannot meet the use requirements; and in the process of toughening and flame retardant modification of its matrix, its mechanical strength is often sacrificed, or while maintaining mechanical strength, the toughness cannot reach a high level, which does not meet the molding performance requirements of the launch tube. Summary of the invention

[0004] This application proposes a flame-retardant high-strength, high-toughness winding epoxy resin composition and a preparation method thereof, aiming to solve the deficiencies of traditional epoxy resin matrix materials in high strength, toughness and flame retardancy through innovative material design and preparation technology, and to provide a new solution for the molding of high-performance composite components such as launch tubes.

[0005] In a first aspect, the present application provides a flame-retardant high-strength, high-toughness winding epoxy resin composition, characterized in that the following technical solution is adopted:

[0006] A flame-retardant high-strength and high-toughness winding epoxy resin composition, comprising an epoxy resin component A and a curing agent component B;

[0007] The epoxy resin component A raw material comprises the following components by weight: 40-50 parts of epoxy resin mixture, 35-45 parts of flame retardant, 8-9 parts of diluent, 6-15 parts of toughening agent, and 0.5-1 parts of surfactant;

[0008] Among them, the toughening agent is a mixture of core-shell rubber and CNTs with a weight ratio of (5-15):(0.2-1). The CNTs are single-walled carbon nanotubes, the dispersion medium is ethoxylated alcohol with an effective content > 80 wt%, the length of the carbon nanotubes is 5-10 μm, and the diameter is 1.5-2.0 nm; the core-shell rubber is at least one of MX-150, MX-154, and MX-160, and the particle size is 100-200 nm;

[0009] The raw materials of the curing agent component B include the following components by weight: 97-100 parts of acid anhydride curing agent and 1-2 parts of accelerator.

[0010] Further, the epoxy resin mixture includes one or a mixture of bisphenol A epoxy resin, bisphenol F epoxy resin, and polyfunctional epoxy resin.

[0011] Further, the bisphenol A epoxy resin includes at least one of E-51, E-54, E-44, E-20, and E-12, the bisphenol F epoxy resin includes NPEF-170, and the polyfunctional epoxy resin includes at least one of AG-80, AFG-90, and TDE-85.

[0012] Further, the flame retardant is brominated epoxy resin with a bromine content of 46-50%.

[0013] Further, the diluent is a mixture of one or more of monofunctional epoxy active diluents, bifunctional epoxy active diluents, and polyfunctional epoxy active diluents. Still further, the diluent is a mixture of one or more of 12-14 alkyl glycidyl ether, butyl glycidyl ether, phenyl glycidyl ether, 1,4-butanediol diglycidyl ether, neopentyl glycol diglycidyl ether, ethylene glycol diglycidyl ether, and 1,6-hexanediol diglycidyl ether.

[0014] Further, the surfactant is a mixture of one or more of BYK-A530, BYK-9920, and KH550.

[0015] Further, the acid anhydride curing agent is a mixture of one or more of methyltetrahydrophthalic anhydride, tetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, hexahydrophthalic anhydride, and methylnadic anhydride.

[0016] Further, the accelerator is a mixture of one or more of imidazoles or tertiary amines. Still further, the accelerator is a mixture of one or more of benzyl ammonium chloride, benzyldimethylamine, N,N-dimethylbenzylamine, 1-methylimidazole, 2-methylimidazole, 2-ethyl-4-methylimidazole, and derivatives of such imidazoles.

[0017] Second aspect, the present application provides a method for preparing a flame-retardant high-strength and high-toughness winding epoxy resin composition, adopting the following technical solutions:

[0018] A method for preparing a flame-retardant high-strength and high-toughness winding epoxy resin composition, comprising the following steps:

[0019] Preparation of component A of the epoxy resin system: Disperse part of the epoxy resin, surfactant and CNTs in a reaction kettle at 80 ± 10 °C at a high speed for 2 - 3 h, with a dispersion speed of 1500 - 2000 rad / min; then raise the temperature to 120 ± 5 °C, add part of the epoxy resin and the flame retardant, adjust the speed to 100 - 200 rad / min, and keep warm for 1.5 - 2.5 h; lower the temperature to 70 ± 10 °C, add the remaining epoxy resin, diluent, and core-shell rubber, and stir for 1 - 2 h at a speed of 200 - 300 rad / min, and cool to room temperature to obtain material A;

[0020] Preparation of component B of the epoxy resin system: Stir the anhydride curing agent and the accelerator by weight at 35 - 55 °C for 30 - 40 min; cool down to 25 - 35 °C to obtain material B;

[0021] Mix material A and material B according to the mass ratio to obtain the epoxy resin composition suitable for preparing the launcher by the winding process.

[0022] In summary, the present application has the following beneficial effects:

[0023] (1) The winding epoxy resin system material prepared in the present application is suitable for the winding molding process of the launcher and can be quickly wound under the conditions of 25 - 45 °C; the cured product of this system material has a Tg ≥ 130 °C, a tensile strength ≥ 80 MPa, a tensile modulus ≥ 3.4 GPa, an elongation at break ≥ 4%, a flame retardant grade up to UL-94V0, and a pot life of 6 - 12 h, meeting the performance requirements of launcher molding.

[0024] (2) This application adopts the method of synergistically enhancing and toughening with core-shell rubber and CNTs. During the resin curing process, the rubber particles present a "sea-island" microphase separation structure. When the material is subjected to external forces, the rubber particles can induce local plastic deformation and absorb a large amount of energy, thereby hindering the crack propagation. Due to the large specific surface area and surface roughness of CNTs, they can enhance the interlayer crack resistance between the resin and fibers or between fibers through the mechanical locking effect in the composite material, and further improve the strength and toughness of the product. The synergy of the two can achieve the simultaneous improvement of the toughness and strength of the resin system. Further, this application synergistically uses a specified type of core-shell rubber and a specified type of carbon nanotube as toughening agents, enabling the "sea-island" microphase separation structure of the core-shell rubber and the mechanical locking effect of the carbon nanotubes to reach a dynamic balance and full cooperation in the epoxy resin system of this application, effectively improving the toughness and strength of the resin system.

[0025] (3) The raw materials of this application are easily available, the process is simple, the cost is low, and the safety is high, making it suitable for process promotion. Detailed implementation mode

[0026] The following further elaborates on this application with reference to examples.

[0027] Example

[0028] The example of this application first provides a flame-retardant high-strength and high-toughness winding epoxy resin composition, including epoxy resin component A and curing agent component B with a weight ratio of 100:(80 - 85).

[0029] Among them, the raw materials of epoxy resin component A include the following components by weight: 40 - 50 parts of epoxy resin mixture, 35 - 45 parts of flame retardant, 8 - 9 parts of diluent, 6 - 15 parts of toughening agent, and 0.5 - 1 part of surfactant.

[0030] The epoxy resin mixture includes one or a mixture of bisphenol A epoxy resin, bisphenol F epoxy resin, and multi-functional epoxy resin. Preferably, the bisphenol A epoxy resin includes at least one of E-51, E-54, E-44, E-20, and E-12, the bisphenol F epoxy resin includes NPEF-170, and the multi-functional epoxy resin includes at least one of AG-80, AFG-90, and TDE-85.

[0031] The toughening agent is a mixture of core-shell rubber and CNTs with a weight ratio of (5 - 15):(0.2 - 1). The CNTs are single-walled carbon nanotubes, the dispersion medium is ethoxylated alcohol, the effective content > 80wt%, the carbon nanotube length is 5 - 10μm, and the diameter is 1.5 - 2.0nm; the core-shell rubber is at least one of MX-150, MX-154, and MX-160, and the particle size is 100 - 200nm.

[0032] The flame retardant is a brominated epoxy resin with a bromine content of 46 - 50%.

[0033] The diluent is one or a mixture of several of a monofunctional epoxy active diluent, a bifunctional epoxy active diluent, and a polyfunctional epoxy active diluent. Preferably, the diluent used in the embodiments of the present application is a mixture of one or several of 12 - 14 alkyl glycidyl ether, butyl glycidyl ether, phenyl glycidyl ether, 1,4 - butanediol diglycidyl ether, neopentyl glycol diglycidyl ether, ethylene glycol diglycidyl ether, and 1,6 - hexanediol diglycidyl ether.

[0034] The surfactant is a mixture of one or several of BYK - A530, BYK - 9920, and KH550.

[0035] Among them, the raw materials of the B component of the curing agent include the following components by weight parts: 97 - 100 parts of an acid anhydride curing agent and 1 - 2 parts of an accelerator.

[0036] The acid anhydride curing agent is a mixture of one or several of methyltetrahydrophthalic anhydride, tetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, hexahydrophthalic anhydride, and methylnadic anhydride.

[0037] The accelerator is a mixture of one or several of imidazoles or tertiary amines. Preferably, the accelerator used in this embodiment is a mixture of one or several of benzyl ammonium chloride, benzyldimethylamine, N,N - dimethylbenzylamine, 1 - methylimidazole, 2 - methylimidazole, 2 - ethyl - 4 - methylimidazole, and derivatives of such imidazoles.

[0038] The embodiments of the present application also provide a preparation method of a flame - retardant high - strength and high - toughness winding epoxy resin composition, including the following steps:

[0039] Preparation of the A component of the epoxy resin system: High - speed disperse part of the epoxy resin, surfactant, and CNTs in a reaction kettle at 80 ± 10°C for 2 - 3 h, with a dispersion speed of 1500 - 2000 rad / min; then raise the temperature to 120 ± 5°C, add part of the epoxy resin and the flame retardant, adjust the speed to 100 - 200 rad / min, and keep warm for 1.5 - 2.5 h; lower the temperature to 70 ± 10°C, add the remaining epoxy resin, diluent, and core - shell rubber, and stir at a speed of 200 - 300 rad / min for 1 - 2 h, and cool to room temperature to obtain the A material;

[0040] Preparation of the B component of the epoxy resin system: Stir the acid anhydride curing agent and the accelerator by weight parts at 35 - 55°C for 30 - 40 min; cool down to 25 - 35°C to obtain the B material;

[0041] Mix materials A and B according to the mass ratio to obtain the epoxy resin composition suitable for preparing the launcher by the winding process.

[0042] Specifically, in Examples 1-5 of the present application, the preparation method of the flame-retardant, high-strength, and high-toughness winding epoxy resin composition includes the following steps:

[0043] Preparation of component A of the epoxy resin system: Disperse part of the epoxy resin, surfactant, and CNTs in a reaction kettle at 80 ± 10 °C at a high speed for 2.5 h, with a dispersion speed of 1800 rad / min; then raise the temperature to 120 ± 5 °C, add part of the epoxy resin and the flame retardant, adjust the speed to 180 rad / min, and keep warm for 2 h; lower the temperature to 70 ± 10 °C, add the remaining epoxy resin, diluent, and core-shell rubber, and stir for 2 h at a speed of 280 rad / min, and cool to room temperature to obtain material A;

[0044] Preparation of component B of the epoxy resin system: Stir the anhydride curing agent and accelerator in parts by weight at 35-55 °C for 40 min; cool to 25-35 °C to obtain material B.

[0045] The following is explained through specific examples.

[0046] Example 1

[0047] This example provides a flame-retardant, high-strength, and high-toughness winding epoxy resin composition, which is divided into component A of the epoxy resin and curing agent B component. The weight ratio of component A of the epoxy resin to curing agent B component is 100:85.

[0048] The raw materials of component A of the epoxy resin include the following components in parts by weight: 40 parts of epoxy resin mixture, 40 parts of flame retardant, 8 parts of diluent, 15 parts of toughening agent, and 0.5 part of surfactant.

[0049] The raw materials of curing agent B component include the following components in parts by weight: 40 parts of methyltetrahydrophthalic anhydride, 57 parts of methylhexahydrophthalic anhydride, and 2 parts of N,N-dimethylbenzylamine.

[0050] Among them, the epoxy resin mixture is 32 parts of epoxy resin E54 and 8 parts of AFG90.

[0051] The toughening agent is a mixture of core-shell rubber and CNTs with a mass ratio of (14.8):(0.2); the polybutadiene-poly(methyl methacrylate) core-shell toughening agent is specifically MX-160;

[0052] The diluent is 1,4-butanediol diglycidyl ether, and the surfactant is BYK-A530.

[0053] Example 2

[0054] This embodiment provides a flame-retardant high-strength and high-toughness winding epoxy resin composition, which is divided into epoxy resin component A and curing agent component B. The weight ratio of epoxy resin component A to curing agent component B is 100:85.

[0055] The raw materials of epoxy resin component A include the following components by weight: 50 parts of epoxy resin mixture, 35 parts of flame retardant, 9 parts of diluent, 6 parts of toughening agent, and 1 part of surfactant.

[0056] The raw materials of curing agent component B include the following components by weight: 60 parts of methyltetrahydrophthalic anhydride, 39 parts of methylnadic anhydride, and 1 part of 2-ethyl-4-methylimidazole.

[0057] Among them, the epoxy resin mixture is 34 parts of E54, 9 parts of TDE-85, and 7 parts of E20.

[0058] The toughening agent is a mixture of core-shell rubber and CNTs with a mass ratio of (5):(1); the specific core-shell toughening agent is MX150.

[0059] The diluent is 1,4-butanediol diglycidyl ether, and the surfactant is 0.5 part of BYK-9920 and 0.5 part of KH550.

[0060] Example 3

[0061] This embodiment provides a flame-retardant high-strength and high-toughness winding epoxy resin composition, which is divided into epoxy resin component A and curing agent component B. The weight ratio of epoxy resin component A to curing agent component B is 100:80.

[0062] The raw materials of epoxy resin component A include the following components by weight: 45 parts of epoxy resin mixture, 36 parts of flame retardant, 9 parts of diluent, 10.5 parts of toughening agent, and 1 part of surfactant.

[0063] The raw materials of curing agent component B include the following components by weight: 80 parts of methylhexahydrophthalic anhydride, 19 parts of methylnadic anhydride, and 1 part of 2-methylimidazole.

[0064] Among them, the epoxy resin mixture is 36 parts of epoxy resin E54, 5 parts of AG-80, and 4 parts of E12.

[0065] The toughening agent is a mixture of core-shell rubber and CNTs with a mass ratio of (10):(0.5); the specific core-shell toughening agent is MX154.

[0066] The diluent is C12-14 alkyl glycidyl ether, and the surfactant is 0.5 part of BYK-9920 and 0.5 part of KH550.

[0067] Example 4

[0068] This embodiment provides a flame-retardant high-strength and high-toughness winding epoxy resin composition, which is divided into epoxy resin component A and curing agent component B. The weight ratio of epoxy resin component A to curing agent component B is 100:80.

[0069] The raw materials of epoxy resin component A include the following components by weight: 40 parts of epoxy resin mixture, 45 parts of flame retardant, 9 parts of diluent, 10.5 parts of toughening agent, and 1 part of surfactant.

[0070] The raw materials of curing agent component B include the following components by weight: 38 parts of methylhexahydrophthalic anhydride, 60 parts of methylnadic anhydride, and 1 part of 2-ethyl-4-methylimidazole.

[0071] Among them, the epoxy resin mixture is 40 parts of epoxy resin E54.

[0072] The toughening agent is a mixture of core-shell rubber and CNTs with a mass ratio of (10):(0.5); the core-shell toughening agent is specifically MX160.

[0073] The diluent is C12 - 14 alkyl glycidyl ether, and the surfactant is 0.5 part of BYK-9920 and 0.5 part of KH550.

[0074] Example 5

[0075] This embodiment provides a flame-retardant high-strength and high-toughness winding epoxy resin composition, which is divided into epoxy resin component A and curing agent component B. The weight ratio of epoxy resin component A to curing agent component B is 100:80.

[0076] The raw materials of epoxy resin component A include the following components by weight: 40 - 50 parts of epoxy resin mixture, 40 parts of flame retardant, 8 parts of diluent, 11 parts of toughening agent, and 1 part of surfactant.

[0077] The raw materials of curing agent component B include the following components by weight: 80 parts of methylhexahydrophthalic anhydride, 20 parts of methylnadic anhydride, and 1 part of 1-methylimidazole.

[0078] Among them, the epoxy resin mixture is 50 parts of epoxy resin E54.

[0079] The toughening agent is a mixture of core-shell rubber and CNTs with a mass ratio of (10):(1); the core-shell toughening agent is specifically MX154.

[0080] The diluent is 1,4-butanediol diglycidyl ether, and the surfactant is 0.5 part of BYK-9920 and 0.5 part of KH550.

[0081] Comparative Example

[0082] The difference between Comparative Example 1 and Example 1 lies in that in the toughening agent, the carbon nanotubes are replaced with an equal amount of core-shell rubber.

[0083] The difference between Comparative Example 2 and Example 1 lies in that in the toughening agent, no core-shell rubber is added.

[0084] The difference between Comparative Example 3 and Example 1 lies in that in the toughening agent, the core-shell rubber is replaced with an equal amount of carboxyl-terminated butadiene acrylonitrile rubber (CTBN).

[0085] The difference between Comparative Example 4 and Example 1 lies in that in the toughening agent, the core-shell rubber is replaced with polyether polyol HM6300.

[0086] The difference between Comparative Example 5 and Example 1 lies in that in the toughening agent, the carbon nanotubes are multi-walled carbon nanotubes (MWNT), the length of the carbon nanotubes is 30 - 50 μm, and the diameter is 1 - 8 nm.

[0087] The difference between Comparative Example 6 and Example 1 lies in that the toughening agent is 5 parts of core-shell rubber and 2 parts of CNTs.

[0088] Performance testing

[0089] Performance testing was carried out on the epoxy resin compositions obtained in the examples and comparative examples, and the test results are shown in Table 1. In addition, for the epoxy resin composition obtained in Example 4, a composite material was prepared according to standard JC / T 773, with the carbon fiber being T700, and its interlaminar shear strength was detected to be 84 MPa.

[0090] Table 1 Performance test results of examples and comparative examples

[0091]

[0092] First, according to the performance test data of Examples 1 - 5, it can be seen that the epoxy resin composition of the present application has good mechanical properties, toughness and flame retardancy. Its Tg ≥ 130 °C, tensile strength ≥ 80 MPa, tensile modulus ≥ 3.4 GPa, elongation at break ≥ 4%, the flame retardancy grade can reach UL-94V0, and the pot life is 6 - 12 h, meeting the performance requirements for launcher molding.

[0093] Regarding the excellent performance obtained in the present application, the following analysis is made in combination with the comparative examples:

[0094] Combining the performance tests of Comparative Examples 1 and 2, it can be seen that although the Tg, flame retardant properties and application period of Comparative Example 1 are not affected too much due to the lack of carbon nanotubes, its mechanical properties and toughness have decreased to varying degrees. Comparative Example 2 has a significant decrease in toughness and a certain decrease in mechanical properties due to the lack of shell-core rubber. In theory, rubber-like substances mainly improve toughness and have a certain negative effect on mechanical properties. The decrease in mechanical properties of Comparative Example 2 shows that the use of carbon nanotubes alone cannot improve the mechanical properties of the resin system of this application. This shows that in the toughening agent system, carbon nanotubes and shell-core rubber work synergistically to make the resin have both good mechanical properties and toughness.

[0095] In view of the synergistic effect of carbon nanotubes and core-shell rubber, the performance of comparative examples 3 to 5 is further analyzed, among which, comparative example 3 uses other types of rubber, comparative example 4 uses other types of toughening agents, and comparative example 5 uses carbon nanotubes of other sizes and shapes. It can be seen that neither other types of rubber nor toughening agents can achieve the same effect as the present application. In addition, the use of carbon nanotubes of other shapes and sizes cannot achieve the performance improvement of the resin system of the present application. This is because the core-shell rubber and carbon nanotubes used in the present application realize the synergy of the "island" microphase separation structure of the core-shell rubber and the mechanical locking effect of the carbon nanotubes, which achieve dynamic balance and full coordination in the epoxy resin system of the present application, effectively improving the toughness and strength of the resin system. In addition, according to the performance of comparative example 6, in the synergistic effect of the carbon nanotubes and core-shell rubber in the present application, the dosage ratio of the two is also very important.

[0096] This specific embodiment is merely an explanation of the present application and is not a limitation of the present application. After reading this specification, those skilled in the art may make modifications to the present embodiment without any creative contribution as needed, but such modifications are protected by the patent law as long as they are within the scope of the claims of the present application.

Claims

1. A flame retardant high-strength, high-toughness winding epoxy resin composition, characterized in that: It includes epoxy resin component A and curing agent component B; The epoxy resin component A raw material comprises the following components by weight: 40-50 parts of epoxy resin mixture, 35-45 parts of flame retardant, 8-9 parts of diluent, 6-15 parts of toughening agent, and 0.5-1 parts of surfactant; The toughening agent is a mixture of core-shell rubber and CNTs in a weight ratio of (5-15): (0.2-1), the CNTs are single-walled carbon nanotubes, the dispersion medium is ethoxylated alcohol, the effective content is >80wt%, the carbon nanotubes are 5-10μm long, and the diameter is 1.5-2.0nm; the core-shell rubber is at least one of MX-150, MX-154, and MX-160, and the particle size is 100-200nm; The raw materials of curing agent component B include the following components by weight: 97-100 parts of anhydride curing agent and 1-2 parts of accelerator.

2. A flame-retardant high-strength, high-toughness winding epoxy resin composition according to claim 1, characterized in that: The epoxy resin mixture includes one or a mixture of bisphenol A epoxy resin, bisphenol F epoxy resin, and multifunctional epoxy resin.

3. A flame-retardant high-strength, high-toughness winding epoxy resin composition according to claim 1, characterized in that: The bisphenol A type epoxy resin includes at least one of E-51, E-54, E-44, E-20, and E-12, the bisphenol F type epoxy resin includes NPEF-170, and the multifunctional epoxy resin includes at least one of AG-80, AFG-90, and TDE-85.

4. A flame-retardant high-strength, high-toughness winding epoxy resin composition according to claim 1, characterized in that: The flame retardant is brominated epoxy resin with a bromine content of 46-50%.

5. A flame-retardant high-strength, high-toughness winding epoxy resin composition according to claim 1, characterized in that: The diluent is one or a mixture of monofunctional epoxy reactive diluent, difunctional epoxy reactive diluent and multifunctional epoxy reactive diluent.

6. A flame-retardant high-strength, high-toughness winding epoxy resin composition according to claim 1, characterized in that: The surfactant is one of BYK-A530, BYK-9920 and KH550 or a mixture of several thereof.

7. A flame-retardant high-strength, high-toughness winding epoxy resin composition according to claim 1, characterized in that: The acid anhydride curing agent is one of methyltetrahydrophthalic anhydride, tetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, hexahydrophthalic anhydride and methylnadic anhydride or a mixture of several of them.

8. The flame-retardant high-strength and high-toughness winding epoxy resin composition according to claim 1, characterized in that: The accelerator is one or a mixture of several imidazoles or tertiary amines.

9. A method for preparing a flame-retardant high-strength, high-toughness winding epoxy resin composition as claimed in any one of claims 1 to 8, characterized in that: The following steps are involved: Preparation of component A of epoxy resin system: disperse part of epoxy resin, surfactant and CNTs in a reactor at 80±10℃ at high speed for 2-3h, with a dispersion speed of 1500-2000rad / min; then heat to 120±5℃, add part of epoxy resin and flame retardant, adjust the speed to 100-200rad / min, and keep warm for 1.5-2.5h; lower the temperature to 70±10℃, add the remaining epoxy resin, diluent, shell-core rubber, stir for 1-2h at a speed of 200-300rad / min, and cool to room temperature to obtain material A; Preparation of epoxy resin system component B: stir the anhydride curing agent and the accelerator according to weight at 35-55° C. for 30-40 minutes; cool to 25-35° C. to obtain material B; The material A and the material B are mixed according to a mass ratio to obtain an epoxy resin composition suitable for preparing a launching tube by a winding process.

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