Epoxy resin composite material as well as preparation method and application thereof

Abstract

The invention belongs to the technical field of coatings, and particularly relates to an epoxy resin composite material and a preparation method and application thereof. The epoxy resin composite material is prepared from the following raw materials: a fluorosilane coupling agent, hydrophobic fumed silica, first epoxy resin and second epoxy resin, the second epoxy resin comprises the following raw materials: high-epoxy-equivalent epoxy resin, low-epoxy-equivalent epoxy resin and flexible epoxy resin. The epoxy resin composite material has the beneficial effects that due to introduction of hydrophobic silicon dioxide and fluorine-containing groups, the self-cleaning performance and the ultraviolet stability of a coating are remarkably improved; chemical bonding and physical entanglement among resin components are accurately regulated and controlled, so that the mechanical strength and toughness of the coating are synergistically enhanced.

Description

TECHNICAL FIELD

[0001] The application belongs to the technical field of coatings, and particularly relates to an epoxy resin composite material and a preparation method and application thereof. BACKGROUND

[0002] Epoxy resin coatings have excellent adhesion, chemical corrosion resistance and mechanical strength, and are widely used in surface protection in the fields of construction, automobiles, ships and the like. However, the traditional epoxy resin coating is poor in hydrophobicity when used outdoors for a long time, leading to the adhesion of pollutants, and the rigid molecular chain structure of the coating is prone to degradation and brittle under ultraviolet radiation, resulting in poor impact resistance, and thus the coating cannot meet the long-term service requirements in harsh environments. The prior art adds silica fillers to increase the hydrophobicity of the coating, but the silica fillers have poor interface compatibility with the resin matrix, and thus cannot form a stable super-hydrophobic structure.

[0003] The prior art also uses a silane coupling agent to modify nano-silica to enhance the hydrophobicity of the epoxy resin coating, but the self-cleaning ability of the coating obtained is limited and the hydrophobic stability is insufficient, and the contact angle decreases by more than 30% after 200h of ultraviolet aging. The prior art also adds a flexible polyurethane prepolymer to improve the toughness of the coating, but excessive addition leads to a decrease in the glass transition temperature of more than 15℃, which seriously affects the hardness of the coating. The prior art also uses a two-component epoxy resin system to balance the mechanical properties, but simple blending of the epoxy resin leads to phase separation. SUMMARY

[0004] The application provides an epoxy resin composite material and a preparation method and application thereof, and aims to solve the problems of insufficient hydrophobicity and self-cleaning ability, weak ultraviolet aging resistance and poor mechanical strength of the existing epoxy resin.

[0005] The first aspect of the application provides an epoxy resin composite material, comprising the following raw materials: a fluorosilane coupling agent, hydrophobic fumed silica, a first epoxy resin and a second epoxy resin.

[0006] The second epoxy resin comprises the following raw materials: a high epoxy equivalent weight epoxy resin, a low epoxy equivalent weight epoxy resin and a flexible epoxy resin.

[0007] According to some embodiments of the epoxy resin composite material of the application, the mass ratio of the fluorosilane coupling agent to the hydrophobic fumed silica is (1-4):100.

[0008] According to some embodiments of the epoxy resin composite material of the application, the mass ratio of the hydrophobic fumed silica to the first epoxy resin is (2-5):50.

[0009] According to some embodiments of the epoxy resin composite material described herein, the mass ratio of the first epoxy resin to the second epoxy resin is 1:(1-5).

[0010] According to some embodiments of the epoxy resin composite material described in this application, the second epoxy resin includes the following raw materials in parts by weight: 50-70 parts of a high epoxy equivalent weight epoxy resin, 10-30 parts of a low epoxy equivalent weight epoxy resin, and 10-20 parts of a flexible epoxy resin.

[0011] According to some embodiments of the epoxy resin composite material described herein, the fluorosilane coupling agent includes tridecafluorooctyltriethoxysilane and / or heptadecafluorodecyltrimethoxysilane.

[0012] According to some embodiments of the epoxy resin composite material described herein, the first epoxy resin includes bisphenol A epoxy resin and / or novolac epoxy resin.

[0013] According to some embodiments of the epoxy resin composite material described in the present application, the high epoxy equivalent weight epoxy resin includes one or more of E-09 bisphenol A epoxy resin, E-03 bisphenol A epoxy resin and E-12 bisphenol A epoxy resin.

[0014] According to some embodiments of the epoxy resin composite material described in the present application, the low epoxy equivalent weight epoxy resin includes one or more of E-51 bisphenol A epoxy resin, E-44 bisphenol A epoxy resin and bisphenol F epoxy resin.

[0015] According to some embodiments of the epoxy resin composite material described herein, the particle size of the hydrophobic fumed silica is 30-150 nm.

[0016] According to some embodiments of the epoxy resin composite material described in this application, the epoxy equivalent of the high epoxy equivalent weight epoxy resin is 800-3000 g / eq.

[0017] According to some embodiments of the epoxy resin composite material described herein, the epoxy equivalent of the low epoxy equivalent weight epoxy resin is 180-300 g / eq.

[0018] According to some embodiments of the epoxy resin composite material described herein, the number of continuous methylene structural units contained in the flexible epoxy resin is ≥8.

[0019] According to some embodiments of the epoxy resin composite material described herein, the flexible epoxy resin includes itaconic acid epoxy resin.

[0020] According to some embodiments of the epoxy resin composite material described herein, the flexible epoxy resin includes polyurethane-modified epoxy resin and / or silicone-modified epoxy resin.

[0021] According to some embodiments of the epoxy resin composite material described in the present application, it further includes an amine curing agent, and the molar ratio of the amine hydrogen in the amine curing agent to the molar ratio of the epoxy group in the epoxy resin composite material is (0.8-1.2):1.

[0022] According to some embodiments of the epoxy resin composite material of the present application, a UV absorber is further included, and the amount of the UV absorber added is 0.5-3 wt % of the mass of the epoxy resin composite material.

[0023] The second aspect of the present application provides a method for preparing the epoxy resin composite material according to the first aspect of the present application, comprising the following steps:

[0024] (1) using a fluorosilane coupling agent to modify hydrophobic fumed silica to obtain modified silica;

[0025] (2) mixing the modified silica and the first epoxy resin to perform a chemical grafting reaction to obtain a first modified epoxy resin;

[0026] (3) The first modified epoxy resin, the high epoxy equivalent weight epoxy resin, the low epoxy equivalent weight epoxy resin, the flexible epoxy resin, and optionally a curing agent and an ultraviolet absorber are mixed to obtain the epoxy resin composite material.

[0027] According to some embodiments of the method for preparing the epoxy resin composite material described in the present application, in step (1), the modification treatment includes mixing the fluorosilane coupling agent, hydrophobic fumed silica and solvent at a temperature of 50-70° C. for 3-6 hours.

[0028] According to some embodiments of the method for preparing the epoxy resin composite material described in the present application, the solvent includes one or more of ethanol, methanol, and propanol.

[0029] According to some embodiments of the method for preparing the epoxy resin composite material described in the present application, in step (2), the temperature of the chemical grafting reaction is 80-120° C., and the time of the chemical grafting reaction is 2-4 hours.

[0030] According to some embodiments of the method for preparing the epoxy resin composite material described in the present application, the chemical grafting reaction is performed in an inert atmosphere.

[0031] The third aspect of the present application provides an application of the epoxy resin composite material described in the first aspect of the present application or the epoxy resin composite material obtained by the preparation method described in the second aspect of the present application in building exterior walls, automobile topcoat or ship protective coating.

[0032] The beneficial effects of the present application include: the introduction of hydrophobic silica and fluorine-containing groups in the epoxy resin composite material described in the present application significantly improves the self-cleaning performance and UV stability of the coating; by precisely controlling the chemical bonding and physical entanglement between the resin components, the mechanical strength and toughness of the coating are synergistically enhanced. DETAILED DESCRIPTION

[0033] The embodiments of the present invention are described in detail below. The examples of the embodiments are exemplary and intended to be used to explain the present invention, but should not be understood as limiting the present invention.

[0034] In the present invention, the terms "one embodiment", "some embodiments", "examples", "specific examples", or "some examples" mean that the specific features, structures, materials, or characteristics described in conjunction with the embodiment or example are included in at least one embodiment or example of the present invention. In this specification, the schematic expressions of the above terms do not necessarily refer to the same embodiment or example. Moreover, the specific features, structures, materials, or characteristics described can be combined in any one or more embodiments or examples in a suitable manner. In addition, those skilled in the art can combine and combine different embodiments or examples described in this specification and the features of different embodiments or examples without contradiction.

[0035] The present application provides an epoxy resin composite material, comprising the following raw materials: a fluorosilane coupling agent, hydrophobic fumed silica, a first epoxy resin, and a second epoxy resin;

[0036] The second epoxy resin comprises the following raw materials: a high epoxy equivalent weight epoxy resin, a low epoxy equivalent weight epoxy resin, and a flexible epoxy resin. By compounding the high epoxy equivalent weight resin, the low epoxy equivalent weight resin, and the flexible resin, coating performance can be optimized, taking into account crosslinking density, toughness, adhesion, and workability.

[0037] In some embodiments of the present application, the mass ratio of the fluorosilane coupling agent to the hydrophobic fumed silica is (1-4):10, for example, 1:10, 2:10, 3:10, 4:10, etc.

[0038] In some embodiments of the present application, the mass ratio of the hydrophobic fumed silica to the first epoxy resin is (1-4):50; for example, 1:10, 2:10, 3:10, 4:10, etc.

[0039] In some embodiments of the present application, the mass ratio of the first epoxy resin to the second epoxy resin is 1:(1-5); for example, 1:1, 1:2, 1:4, 1:5, etc.

[0040] In some embodiments of the present application, the second epoxy resin comprises the following raw materials in parts by weight: 50-70 parts high epoxy equivalent weight epoxy resin, 10-30 parts low epoxy equivalent weight epoxy resin, and 10-20 parts flexible epoxy resin. By compounding the high epoxy equivalent weight epoxy resin, the low epoxy equivalent weight epoxy resin, and the flexible epoxy resin, coating performance can be optimized, taking into account crosslinking density, toughness, adhesion, and workability.

[0041] In some embodiments of the present application, the second epoxy resin includes the following raw materials in parts by weight: 53-68 parts of a high epoxy equivalent weight epoxy resin, 12-26 parts of a low epoxy equivalent weight epoxy resin, and 12-18 parts of a flexible epoxy resin.

[0042] In some embodiments of the present application, the second epoxy resin includes the following raw materials in parts by weight: 58-63 parts of a high epoxy equivalent weight epoxy resin, 15-22 parts of a low epoxy equivalent weight epoxy resin, and 13-15 parts of a flexible epoxy resin.

[0043] In some embodiments of the present application, the fluorosilane coupling agent includes tridecafluorooctyltriethoxysilane and / or heptadecafluorodecyltrimethoxysilane; the use of a fluorosilane coupling agent can introduce fluorine-containing groups to enhance the UV aging resistance of the coating.

[0044] In some embodiments of the present application, the first epoxy resin includes bisphenol A epoxy resin and / or novolac epoxy resin.

[0045] In some embodiments of the present application, the high epoxy equivalent weight epoxy resin includes one or more of E-09 bisphenol A epoxy resin, E-03 bisphenol A epoxy resin, and E-12 bisphenol A epoxy resin.

[0046] In some embodiments of the present application, the low epoxy equivalent weight epoxy resin includes one or more of E-51 bisphenol A epoxy resin, E-44 bisphenol A epoxy resin, and bisphenol F epoxy resin;

[0047] In some embodiments of the present application, the particle size of the hydrophobic fumed silica is 30-150 nm; for example, 30 nm, 50 nm, 68 nm, 73 nm, 89 nm, 96 nm, 106 nm, 117 nm, 126 nm, 132 nm, 148 nm, 150 nm, etc.

[0048] In some embodiments of the present application, the epoxy equivalent of the high epoxy equivalent weight epoxy resin is 800-3000 g / eq; for example, 800 g / eq, 1000 g / eq, 1450 g / eq, 1860 g / eq, 2010 g / eq, 2380 g / eq, 2730 g / eq, 2810 g / eq, 3000 g / eq, etc.

[0049] In some embodiments of the present application, the epoxy equivalent of the low epoxy equivalent weight epoxy resin is 180-300 g / eq; for example, 180 g / eq, 200 g / eq, 220 g / eq, 250 g / eq, 270 g / eq, 300 g / eq, etc.

[0050] In some embodiments of the present application, the number of continuous methylene structural units contained in the flexible epoxy resin is ≥8; for example, 8, 9, 10, 11, 12, etc.

[0051] In some embodiments of the present application, the flexible epoxy resin includes one or more of itaconic acid epoxy resin, polyurethane modified epoxy resin and silicone modified epoxy resin.

[0052] In some embodiments of the present application, an amine curing agent is also included.

[0053] In some embodiments of the present application, the amine curing agent includes one or more of ethylenediamine, diethylenetriamine and m-phenylenediamine.

[0054] In some embodiments of the present application, the molar ratio of amine hydrogen in the amine curing agent to the molar ratio of epoxy groups in the epoxy resin composite material is (0.8-1.2):1; for example, 0.8:1, 0.9:1, 1:1, 1.2:1, etc.

[0055] In some embodiments of the present application, an ultraviolet absorber is also included.

[0056] In some embodiments of the present application, the ultraviolet absorber includes a benzotriazole compound or a triazine compound.

[0057] In some embodiments of the present application, the added amount of the ultraviolet absorber is 0.5-3wt% of the mass of the epoxy resin composite material; for example, 0.5wt%, 1.3wt%, 2.2wt%, 2.7wt%, 3.0wt%, etc.

[0058] The present application also provides a method for preparing the epoxy resin composite material according to the first aspect of the present application, comprising the following steps:

[0059] (1) using a fluorosilane coupling agent to modify hydrophobic fumed silica to obtain modified silica;

[0060] (2) mixing the modified silica and the first epoxy resin to perform a chemical grafting reaction to obtain a first modified epoxy resin;

[0061] (3) The first modified epoxy resin, the high epoxy equivalent weight epoxy resin, the low epoxy equivalent weight epoxy resin, the flexible epoxy resin, and optionally a curing agent and an ultraviolet absorber are mixed to obtain the epoxy resin composite material.

[0062] In some embodiments of the present application, in step (1), the modification treatment comprises mixing the fluorosilane coupling agent, hydrophobic fumed silica and solvent at a temperature of 50-70°C, such as 50°C, 55°C, 58°C, 65°C, 70°C, etc., for 3-6 hours; for example, 3 hours, 4 hours, 5 hours, 6 hours, etc.

[0063] In some embodiments of the present application, the solvent includes one or more of ethanol, methanol and propanol.

[0064] In some embodiments of the present application, in step (2), the temperature of the chemical grafting reaction is 80-120°C, for example, 80°C, 90°C, 100°C, 105°C, 112°C, 120°C, etc., and the time of the chemical grafting reaction is 2-4h; for example, 2h, 3h, 4h, etc.

[0065] In some embodiments of the present application, the chemical grafting reaction is carried out in an inert atmosphere, such as a nitrogen atmosphere, an argon atmosphere, etc.

[0066] The present application also provides an embodiment of the epoxy resin composite material described in the first aspect of the present application or the epoxy resin composite material obtained by the preparation method described in the second aspect of the present application for use in building exterior walls, automotive topcoats, or ship protective coatings. The epoxy resin composite material described in the present application has high UV resistance and mechanical properties, which increases the service life of the coating and reduces operation and maintenance costs. Because the composite material described in the present application has high self-cleaning ability, it can improve the aesthetics of the coating surface and further enhance its anti-corrosion performance.

[0067] The technical solution of this application is further described below with reference to specific embodiments.

[0068] Example 1

[0069] A method for preparing an epoxy resin composite material comprises the following steps:

[0070] (1) Preparation of modified silica

[0071] 20 g of tridecafluorooctyltriethoxysilane, 100 g of hydrophobic fumed silica with a particle size of 30-100 nm, and ethanol (in the specific operation, a small amount of water is added to the ethanol as a catalyst, and the volume ratio of ethanol to water is 9:1) are mixed, and the mixture is reacted at 60° C. for 4 h. After the reaction is completed, the reaction solution is centrifuged and dried to obtain modified silica;

[0072] (2) Preparation of modified epoxy resin

[0073] 30g of the modified silica was mixed with 100g of bisphenol A epoxy resin and heated to 90°C under nitrogen atmosphere for 3h to obtain the first modified epoxy resin; FT-IP showed that the CF bond (1240cm -1 ) and Si-OC bond (1080cm -1 );

[0074] (3) Preparation of epoxy resin composite materials

[0075] The epoxy resin composite material is obtained by mixing 30 parts of the above-mentioned first modified epoxy resin, 55 parts of E-09 bisphenol A epoxy resin with a high epoxy equivalent weight of 1200 g / eq, 25 parts of E-51 bisphenol A epoxy resin with a low epoxy equivalent weight of 240 g / eq, 20 parts of itaconic acid epoxy resin and 16 parts of polyetheramine D230 curing agent.

[0076] Example 2

[0077] The preparation method of the epoxy resin composite material in Example 2 is different from that in Example 1 only in that the epoxy resin composite material in Example 2 further contains 1.5 parts of ultraviolet absorber UV-234 during the preparation process.

[0078] The specific steps include:

[0079] 30 parts of the first modified epoxy resin, 55 parts of E-09 bisphenol A epoxy resin with a high epoxy equivalent weight of 1200 g / eq, 25 parts of E-51 bisphenol A epoxy resin with a low epoxy equivalent weight of 240 g / eq, 20 parts of itaconic acid epoxy resin, 16 parts of polyetheramine D230 curing agent and 1.5 parts of ultraviolet absorber UV-234 were mixed to obtain the epoxy resin composite material. The remaining operations were the same as in Example 1.

[0080] Example 3

[0081] The preparation method of the epoxy resin composite material described in Example 3 is different from that of Example 1 only in that the amount of the first modified epoxy resin, high epoxy equivalent epoxy resin, low epoxy equivalent epoxy resin and flexible epoxy resin used in the preparation process of the epoxy resin composite material described in Example 3 is different from that in Example 1.

[0082] The specific operation steps include: mixing 30 parts of the above-mentioned first modified epoxy resin, 65 parts of E-09 bisphenol A type epoxy resin with a high epoxy equivalent weight of 1200 g / eq, 17 parts of E-51 bisphenol A type epoxy resin with a low epoxy equivalent weight of 240 g / eq, 18 parts of itaconic acid epoxy resin and 13.5 parts of polyetheramine D230 curing agent to obtain the epoxy resin composite material.

[0083] Example 4

[0084] The preparation method of the epoxy resin composite material described in Example 4 is different from that in Example 1 only in that the amount of the first modified epoxy resin, high epoxy equivalent epoxy resin, low epoxy equivalent epoxy resin and flexible epoxy resin used in the preparation process of the epoxy resin composite material described in Example 4 is different from that in Example 1.

[0085] The specific operation steps include: mixing 45 parts of the above-mentioned first modified epoxy resin, 55 parts of E-09 bisphenol A epoxy resin with a high epoxy equivalent weight of 1200 g / eq, 25 parts of E-51 bisphenol A epoxy resin with a low epoxy equivalent weight of 240 g / eq, 20 parts of itaconic acid epoxy resin and 15 parts of polyetheramine D230 curing agent to obtain the epoxy resin composite material.

[0086] Example 5

[0087] The preparation method of the epoxy resin composite material described in Example 5 is different from that of Example 1 only in that the amount of the first modified epoxy resin, high epoxy equivalent epoxy resin, low epoxy equivalent epoxy resin and flexible epoxy resin used in the preparation process of the epoxy resin composite material described in Example 5 is different from that in Example 1.

[0088] The specific operation steps include: mixing 65 parts of the above-mentioned first modified epoxy resin, 55 parts of E-09 bisphenol A type epoxy resin with a high epoxy equivalent weight of 1200 g / eq, 25 parts of E-51 bisphenol A type epoxy resin with a low epoxy equivalent weight of 240 g / eq, 20 parts of itaconic acid epoxy resin and 15.5 parts of polyetheramine D230 curing agent to obtain the epoxy resin composite material.

[0089] Example 6

[0090] The preparation method of the epoxy resin composite material described in Example 6 is different from that of Example 1 only in that the epoxy equivalent of the high epoxy equivalent weight epoxy resin in the preparation process of the epoxy resin composite material described in Example 6 is 2000 g / eq.

[0091] Example 7

[0092] The preparation method of the epoxy resin composite material described in Example 7 is different from that of Example 1 only in that the epoxy equivalent of the high epoxy equivalent weight epoxy resin in the preparation process of the epoxy resin composite material described in Example 8 is 3000 g / eq.

[0093] Example 8

[0094] The preparation method of the epoxy resin composite material described in Example 8 is different from that of Example 1 only in that the epoxy equivalent of the low epoxy equivalent weight epoxy resin in the preparation process of the epoxy resin composite material described in Example 9 is 180 g / eq.

[0095] Example 9

[0096] The preparation method of the epoxy resin composite material described in Example 9 is different from that of Example 1 only in that the epoxy equivalent of the low epoxy equivalent weight epoxy resin in the preparation process of the epoxy resin composite material described in Example 11 is 300 g / eq.

[0097] Comparative Example 1

[0098] The preparation method of the epoxy resin composite material described in Comparative Example 1 is different from that of Example 1 only in that γ-aminopropyltriethoxysilane coupling agent is used instead of tridecafluorooctyltriethoxysilane during the preparation process of the epoxy resin composite material described in Comparative Example 1.

[0099] Comparative Example 2

[0100] The preparation method of the epoxy resin composite material described in Comparative Example 2 is different from that of Example 1 only in that bisphenol A epoxy resin is used instead of itaconic acid epoxy resin during the preparation process of the epoxy resin composite material described in Comparative Example 2.

[0101] Comparative Example 3

[0102] The preparation method of the epoxy resin composite material described in Comparative Example 3 is different from that of Example 1 only in that, during the preparation process of the epoxy resin composite material described in Comparative Example 3, the modified silica, high epoxy equivalent epoxy resin, low epoxy equivalent epoxy resin and flexible epoxy resin are directly mixed.

[0103] The specific steps include:

[0104] The epoxy resin composite material is obtained by mixing 30 parts of modified silica, 55 parts of E-09 bisphenol A epoxy resin with a high epoxy equivalent weight of 1200 g / eq, 25 parts of E-51 bisphenol A epoxy resin with a low epoxy equivalent weight of 240 g / eq, 20 parts of itaconic acid epoxy resin and polyetheramine D230 curing agent.

[0105] Study on the performance of the epoxy resin composite materials described in Examples 1-11 and Comparative Examples 1-3 of the present application

[0106] Test method:

[0107] The contact angles described in the examples of this application were measured using a contact angle tester produced by Dataphysics in Germany;

[0108] The corrosion resistance test method described in the examples of this application is based on ISO 9227;

[0109] The test method for impact strength described in the examples of this application is based on GB / T 1732;

[0110] The adhesion test method described in the examples of this application is based on GB / T 5210;

[0111] The light retention test described in the examples of this application is based on ASTM D6577.

[0112] The results are shown in Table 1.

[0113] Table 1

[0114] Contact angle / ° Salt spray test time / h Impact strength / Kg.cm Adhesion / MPa QUV 500h gloss retention / % Example 1 143 4200 52 9.8 92 Example 2 142 4200 52 9.6 95 Example 3 140 4200 56 10.2 93 Example 4 149 4200 55 9.5 94 Example 5 152 4200 53 8.9 95 Example 6 141 4000 54 9.7 90 Example 7 137 4000 53 10.0 87 Example 8 146 4200 51 9.7 93 Example 9 144 4200 50 9.4 91 Comparative Example 1 132 3200 45 9.2 81 Comparative Example 2 144 4000 42 8.1 90 Comparative Example 3 127 3000 36 7.7 82

[0115] As can be seen from Table 1, the introduction of hydrophobic silica and fluorine-containing groups into the epoxy resin composite material described in this application significantly improves the self-cleaning performance and UV stability of the coating; by precisely controlling the chemical bonding and physical entanglement between the resin components, the mechanical strength and toughness of the coating are synergistically enhanced.

[0116] Although the above embodiments have been shown and described, it is understood that the above embodiments are illustrative and are not to be construed as limitations on the present invention. Changes, modifications, substitutions and variations of the above embodiments by those skilled in the art are all within the scope of protection of the present invention.

Claims

1. An epoxy resin composite material, characterized in that: The method comprises the following raw materials: a fluorosilane coupling agent, hydrophobic fumed silica, a first epoxy resin and a second epoxy resin; The second epoxy resin comprises the following raw materials: high epoxy equivalent weight epoxy resin, low epoxy equivalent weight epoxy resin and flexible epoxy resin.

2. The epoxy resin composite material according to claim 1, characterized in that: The mass ratio of the fluorosilane coupling agent to the hydrophobic fumed silica is (1-4):10; and / or, the mass ratio of the hydrophobic fumed silica to the first epoxy resin is (1-4):10; And / or, the mass ratio of the first epoxy resin to the second epoxy resin is 1:(1-5).

3. The epoxy resin composite material according to claim 1, characterized in that: The second epoxy resin comprises the following raw materials in parts by weight: 50-70 parts of high epoxy equivalent epoxy resin, 10-30 parts of low epoxy equivalent epoxy resin and 10-20 parts of flexible epoxy resin.

4. The epoxy resin composite material according to claim 1, characterized in that: The fluorosilane coupling agent includes tridecafluorooctyltriethoxysilane and / or heptadecafluorodecyltrimethoxysilane; And / or, the first epoxy resin includes bisphenol A epoxy resin and / or novolac epoxy resin; And / or, the high epoxy equivalent weight epoxy resin includes one or more of E-09 bisphenol A epoxy resin, E-03 bisphenol A epoxy resin and E-12 bisphenol A epoxy resin; And / or, the low epoxy equivalent weight epoxy resin includes one or more of E-51 bisphenol A epoxy resin, E-44 bisphenol A epoxy resin and bisphenol F epoxy resin; And / or, the particle size of the hydrophobic fumed silica is 30-150 nm.

5. The epoxy resin composite material according to claim 1, characterized in that: The epoxy equivalent of the high epoxy equivalent weight epoxy resin is 800-3000 g / eq; And / or, the epoxy equivalent of the low epoxy equivalent weight epoxy resin is 180-300 g / eq; And / or, the number of continuous methylene structural units contained in the flexible epoxy resin is ≥8.

6. The epoxy resin composite material according to claim 5, characterized in that: The flexible epoxy resin includes one or more of itaconic acid epoxy resin, polyurethane modified epoxy resin and organosilicon modified epoxy resin; And / or, further comprising an amine curing agent, wherein the molar ratio of amine hydrogen in the amine curing agent to the molar ratio of epoxy groups in the epoxy resin composite material is (0.8-1.2):1; And / or, it further comprises an ultraviolet absorber, wherein the amount of the ultraviolet absorber added is 0.5-3 wt % of the mass of the epoxy resin composite material.

7. The method for preparing the epoxy resin composite material according to any one of claims 1 to 6, characterized in that: The following steps are involved: (1) using a fluorosilane coupling agent to modify hydrophobic fumed silica to obtain modified silica; (2) mixing the modified silica and the first epoxy resin to perform a chemical grafting reaction to obtain a first modified epoxy resin; (3) The first modified epoxy resin, the high epoxy equivalent weight epoxy resin, the low epoxy equivalent weight epoxy resin, the flexible epoxy resin, and optionally a curing agent and an ultraviolet absorber are mixed to obtain the epoxy resin composite material.

8. The method for preparing the epoxy resin composite material according to claim 7, characterized in that: In step (1), the modification treatment comprises mixing a fluorosilane coupling agent, hydrophobic fumed silica and a solvent at a temperature of 50-70° C. for 3-6 hours; Preferably, the solvent comprises one or more of ethanol, methanol and propanol.

9. The method for preparing the epoxy resin composite material according to claim 7, wherein: In step (2), the temperature of the chemical grafting reaction is 80-120° C., and the time of the chemical grafting reaction is 2-4 hours; And / or, the chemical grafting reaction is carried out in an inert atmosphere.

10. Use of the epoxy resin composite material according to any one of claims 1 to 6 or the epoxy resin composite material obtained by the preparation method according to any one of claims 7 to 9 in building exterior walls, automobile topcoats or ship protective coatings.