Resin matrix toughened with silane coupling agent solution-modified nanomaterial, preparation method therefor, and application thereof

Abstract

The present invention relates to the technical field of composite materials. Provided is a preparation method for a resin matrix toughened with a silane coupling agent solution-modified nanomaterial. A specific silane coupling agent (KH560) solution is used to modify the nanomaterial, which is then used to toughen the resin matrix. KH560 has two reaction groups, which can effectively modify the surface of the nanomaterial and reduce agglomeration, while a molecular chain connecting to the surface of the nanomaterial contains an epoxy group capable of reacting with resin. By means of the molecular chain, efficient bonding between the inorganic nanomaterial and the resin matrix is achieved, the compatibility between the nanomaterial and the resin is improved, and the toughening effect of the nanomaterial on the resin is fully implemented. Moreover, in a curing process, the epoxy group does not occupy a reaction bond position between a curing agent and the resin, improving the post-curing crosslink density of the resin, and further improving the mechanical properties of the resin matrix.

Description

A silane coupling agent solution-modified nanomaterial toughened resin matrix and its preparation method and application Technical Field

[0001] The present invention relates to the technical field of composite materials, and in particular to a silane coupling agent solution-modified nanomaterial toughened resin matrix, a preparation method thereof, and an application thereof. Background Art

[0002] Fiber-reinforced polymer (FRP), a composite material composed of a resin matrix and fibers, exhibits excellent mechanical and corrosion resistance and has been widely used in various fields. In actual engineering applications, the resin matrix is ​​directly exposed to the external environment and protects the fibers. However, it is often brittle and has poor toughness, causing it to prematurely lose its restraint and protective function on the fibers, leading to failure of the FRP composite. Therefore, improving the mechanical properties of the resin matrix is ​​crucial to enhancing the performance of FRP composites.

[0003] Nanomaterials can effectively improve the mechanical properties and toughness of resin matrices. However, due to their large specific surface area and high surface energy, nanoparticles tend to agglomerate, causing internal defects in the matrix. Therefore, improving the compatibility of nanomaterials with the resin matrix is ​​key to fully realizing the reinforcing effect of nanomaterials. Silane coupling agents are commonly used to modify nanomaterials in the prior art, with KH550 being a common silane coupling agent. However, their modification effect is relatively modest. Therefore, further improving the mechanical properties of nanomaterial-modified resin matrices has become a difficult problem in the prior art.

[0004] Summary of the Invention

[0005] The purpose of the present invention is to provide a silane coupling agent solution modified nanomaterial toughened resin matrix and its preparation method and application. The present invention uses KH560 modified nanomaterial to further improve the mechanical properties of the resin matrix.

[0006] In order to achieve the above-mentioned object of the invention, the present invention provides the following technical solutions:

[0007] The present invention provides a method for preparing a nanomaterial toughened resin matrix modified by a silane coupling agent solution, comprising the following steps:

[0008] (1) mixing a silane coupling agent KH560, ethanol, water and acetic acid to carry out a hydrolysis reaction to obtain a silane coupling agent solution;

[0009] (2) mixing the silane coupling agent solution obtained in step (1) with the nanomaterial to perform a modification treatment to obtain a modified nanomaterial;

[0010] (3) The modified nanomaterial obtained in step (2) is mixed with a resin and a curing agent and then cured to obtain a silane coupling agent solution-modified nanomaterial toughened resin matrix.

[0011] Preferably, the mass concentration of the silane coupling agent solution in step (1) is 2-4%.

[0012] Preferably, the pH value of the silane coupling agent solution in step (1) is 4-6.

[0013] Preferably, the nanomaterial in step (2) includes one or more of nano-titanium dioxide and nano-silicon dioxide.

[0014] Preferably, the particle size of the nanomaterial in step (2) is 10 to 20 nm.

[0015] Preferably, in step (2), the mass ratio of the nanomaterial to the silane coupling agent solution is (5-20):100.

[0016] Preferably, the modification treatment time in step (2) is 3 to 6 hours.

[0017] Preferably, in step (3), the mass ratio of the modified nanomaterial to the resin is (1-5):100.

[0018] The present invention provides a silane coupling agent solution-modified nanomaterial toughened resin matrix prepared by the preparation method described in the above technical solution.

[0019] The present invention also provides the use of the silane coupling agent solution-modified nanomaterial toughening resin matrix in the resin-based composite material.

[0020] The invention provides a preparation method of a silane coupling agent solution-modified nanomaterial toughened resin matrix, comprising the following steps: (1) mixing a silane coupling agent KH560, ethanol, water and acetic acid for hydrolysis reaction to obtain a silane coupling agent solution; (2) mixing the silane coupling agent solution obtained in the step (1) with a nanomaterial for modification treatment to obtain a modified nanomaterial; and (3) mixing the modified nanomaterial obtained in the step (2) with a resin and a curing agent and then curing the mixture to obtain a silane coupling agent solution-modified nanomaterial toughened resin matrix. The present invention uses a specific silane coupling agent KH560 solution to modify the nanomaterial and then toughen the resin matrix. KH560 has two reactive groups, which can effectively modify the surface of the nanomaterial and reduce agglomeration. At the same time, the molecular chain connected to the surface of the nanomaterial contains epoxy groups that can react with the resin. Through the molecular chain, efficient connection between the inorganic nanomaterial and the resin matrix can be achieved, the compatibility of the nanomaterial and the resin is improved, and the toughening effect of the nanomaterial on the resin is fully exerted. In addition, during the curing process, the epoxy groups will not occupy the reactive bond between the curing agent and the resin, thereby increasing the crosslinking density of the resin after curing and further improving the mechanical properties of the resin matrix. BRIEF DESCRIPTION OF THE DRAWINGS

[0021] FIG1 is a schematic diagram of the preparation process of a silane coupling agent solution-modified nanomaterial toughened resin matrix according to an embodiment of the present invention;

[0022] FIG2 is a tensile stress-strain curve diagram of the resin matrix prepared in Example 1 and Example 2 of the present invention and Comparative Example 1;

[0023] FIG3 is a tensile stress-strain curve diagram of the resin matrix prepared in Example 3 of the present invention and Comparative Examples 2 to 3. DETAILED DESCRIPTION

[0024] The present invention provides a method for preparing a nanomaterial toughened resin matrix modified by a silane coupling agent solution, comprising the following steps:

[0025] (1) mixing a silane coupling agent KH560, ethanol, water and acetic acid to carry out a hydrolysis reaction to obtain a silane coupling agent solution;

[0026] (2) mixing the silane coupling agent solution obtained in step (1) with the nanomaterial to perform a modification treatment to obtain a modified nanomaterial;

[0027] (3) The modified nanomaterial obtained in step (2) is mixed with a resin and a curing agent and then cured to obtain a silane coupling agent solution-modified nanomaterial toughened resin matrix.

[0028] Unless otherwise specified, the present invention has no particular limitation on the sources of the raw materials, and commercially available products known to those skilled in the art may be used.

[0029] The invention mixes silane coupling agent KH560, ethanol, water and acetic acid for hydrolysis reaction to obtain a silane coupling agent solution.

[0030] In the present invention, the silane coupling agent KH560 (γ-glycidyloxypropyltrimethoxysilane) contains hydrolyzable groups and epoxy groups. The hydrolyzable groups are connected with the nanomaterial after hydrolysis, which can effectively modify the surface of the nanomaterial and reduce agglomeration. At the same time, the epoxy groups can react with the resin matrix without occupying the reactive bond between the curing agent and the resin, thereby increasing the crosslinking density of the resin matrix after curing and improving its mechanical properties.

[0031] In the present invention, the water is preferably deionized water. In the present invention, the mass ratio of the ethanol to water is preferably 1:(0.5-1.5), more preferably 1:1.

[0032] In the present invention, the mass concentration of the silane coupling agent solution is preferably 2-4%, more preferably 2-3%.

[0033] In the present invention, the pH value of the silane coupling agent solution is preferably 4 to 6, more preferably 4 to 5. The present invention has no particular limitation on the amount of acetic acid used, as long as the pH value of the system is within the above range.

[0034] The present invention limits the mass ratio of ethanol to water, the mass concentration of the silane coupling agent solution and the pH value within the above ranges, which is conducive to the full hydrolysis of the silane coupling agent.

[0035] In the present invention, the mixing of the silane coupling agent KH560, ethanol, water and acetic acid is preferably as follows: firstly, ethanol and water are mixed to obtain a mixed solution, then the silane coupling agent KH560 is added, and finally, acetic acid is added to adjust the pH value.

[0036] In the present invention, the hydrolysis reaction time is preferably 20 to 40 minutes, more preferably 30 minutes; the hydrolysis reaction temperature is preferably 20 to 30°C; and the hydrolysis reaction is preferably carried out under stirring. The present invention does not particularly limit the stirring method and rate; stirring methods and rates familiar to those skilled in the art can be used. By limiting the hydrolysis reaction time to the above range, the present invention can ensure sufficient hydrolysis of the silane coupling agent.

[0037] In the present invention, the reaction during the hydrolysis reaction is as shown in Formula I:

[0038] Wherein X is a hydrolyzable group OCH3, Y is an epoxy functional group, and R is a methyl group.

[0039] After obtaining the silane coupling agent solution, the present invention mixes the silane coupling agent solution with the nano material to perform a modification treatment to obtain the modified nano material.

[0040] In the present invention, the nanomaterial preferably includes one or more of nano titanium dioxide and nano silicon dioxide. In the present invention, the specific surface area of ​​the nano titanium dioxide is preferably 20 to 50 m 2 / g; the specific surface area of ​​the nano-silicon dioxide is preferably 220 to 280m 2 / g.

[0041] In the present invention, the particle size of the nanomaterial is preferably 10 to 20 nm, more preferably 15 nm.

[0042] In the present invention, the mass ratio of the nanomaterial to the silane coupling agent solution is preferably (5-20):100, more preferably (10-20):100. By limiting the mass ratio of the nanomaterial to the silane coupling agent solution to the above range, the surface of the nanomaterial can be modified with more silane coupling agent, further improving its modification effect.

[0043] In the present invention, the modification treatment temperature is preferably 20-30°C; the modification treatment duration is preferably 3-6 hours, more preferably 4-5 hours; and the modification treatment is preferably carried out under stirring conditions. The present invention does not specifically limit the stirring method and rate; stirring methods and rates familiar to those skilled in the art can be used. By limiting the modification treatment temperature and duration to the aforementioned ranges, the present invention can further enhance the modification effect of the nanomaterial.

[0044] After the modification treatment is completed, the present invention preferably sequentially washes, filters, dries and grinds the modified product to obtain a modified nanomaterial.

[0045] The present invention has no particular limitation on the operations of washing, filtering, drying and grinding, and the technical solutions of washing, filtering, drying and grinding well known to those skilled in the art may be adopted.

[0046] After obtaining the modified nanomaterial, the present invention mixes the modified nanomaterial with a resin and a curing agent and then cures the mixture to obtain a silane coupling agent solution-modified nanomaterial toughened resin matrix.

[0047] In the present invention, the resin preferably includes epoxy resin or vinyl resin; the epoxy resin is preferably epoxy resin E51.

[0048] When the resin is epoxy resin E51, the curing agent is preferably polyamide resin 650; the mass ratio of epoxy resin E51 to curing agent is preferably 1:(0.5-1.5), more preferably 1:1. When the resin is epoxy resin E51, a defoaming agent is preferably added during mixing; the defoaming agent is preferably a silicone oil or silicone defoaming agent; the mass ratio of the defoaming agent to epoxy resin E51 is preferably (0.1-0.5):100.

[0049] When the resin is a vinyl resin, the curing agent is preferably methyl ethyl ketone peroxide. When the resin is a vinyl resin, an accelerator and a defoamer are preferably added during mixing; the accelerator is preferably cobalt isooctanoate; and the defoamer is preferably a silicone oil or organosilicon defoamer. In the present invention, the mass ratio of the vinyl resin, curing agent, accelerator, and defoamer is preferably 100:(1-3):(0.5-1.5):(0.1-1), and more preferably 100:2:1:0.5.

[0050] In the present invention, the mass ratio of the modified nanomaterial to the resin is preferably (1-5):100, more preferably (2-3):100. By limiting the mass ratio of the modified nanomaterial to the resin to the above range, the nanomaterial can be fully and evenly dispersed in the resin, avoiding agglomeration, and further improving the mechanical properties of the resin matrix.

[0051] In the present invention, the temperature for mixing the modified nanomaterial with the resin and curing agent is preferably 20-30°C; the mixing time is preferably 10-40 minutes, more preferably 15-30 minutes; and the mixing is preferably performed under stirring conditions. The present invention does not particularly limit the stirring method and rate; stirring methods and rates familiar to those skilled in the art can be used.

[0052] In the present invention, the curing temperature is preferably 20-30°C; the curing time is preferably 12-36 hours, more preferably 24 hours. By limiting the curing temperature and time within the above ranges, the present invention can achieve a suitable curing rate for the resin, increase its crosslinking density, and further improve its mechanical properties.

[0053] The flow diagram of the preparation method of the resin matrix toughened by modifying the nanomaterial with a silane coupling agent solution in an embodiment of the present invention is preferably shown in Figure 1: deionized water, a silane coupling agent, anhydrous ethanol and acetic acid are mixed to obtain a silane coupling agent aqueous solution, which is stirred for 30 minutes and then nanoparticles are added. The mixture is stirred for 5 hours, rinsed with anhydrous ethanol, dried in an oven and ground with a grinder to obtain modified nanoparticles, which are then added to the resin for toughening.

[0054] The present invention uses a specific silane coupling agent KH560 to modify the nanomaterial and then toughen the resin matrix. KH560 has two reactive groups, which can effectively modify the surface of the nanomaterial and reduce agglomeration. At the same time, the molecular chain connected to the surface of the nanomaterial contains epoxy groups that can react with the resin. During the curing process, the epoxy groups will not occupy the reactive bond between the curing agent and the resin, thereby increasing the crosslinking density of the resin after curing. By controlling process parameters such as the amount of each component, reaction temperature and time, the mechanical properties of the resin matrix can be further improved.

[0055] The present invention provides a silane coupling agent solution-modified nanomaterial toughened resin matrix prepared by the preparation method described in the above technical solution.

[0056] The resin matrix prepared by the invention has better mechanical properties.

[0057] The present invention also provides the use of the silane coupling agent solution-modified nanomaterial toughening resin matrix in the resin-based composite material.

[0058] The present invention has no special limitation on the application of the silane coupling agent solution-modified nanomaterial to toughen the resin matrix in the resin-based composite material. The technical solutions for the application of the resin matrix in the resin-based composite material well known to those skilled in the art can be adopted.

[0059] The following will be combined with the embodiments of the present invention to clearly and completely describe the technical solutions of the present invention. Obviously, the embodiments described are only some of the embodiments of the present invention, not all of them. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without making creative efforts are within the scope of protection of the present invention.

[0060] Example 1

[0061] (1) 2 g of silane coupling agent KH560 was added to a mixture of 49 g of deionized water and 49 g of anhydrous ethanol (the mass ratio of deionized water to anhydrous ethanol was 1:1), an appropriate amount of acetic acid was added to adjust the pH value to 4-5, and the mixture was stirred at room temperature for 30 min using a magnetic stirrer to obtain a silane coupling agent solution with a mass concentration of 2% (the amount of acetic acid used was very small and would not affect the concentration of the silane coupling agent solution);

[0062] (2) 20g of nano titanium dioxide (particle size 15nm, specific surface area 20-50m 2 / g) was added to 100 g of silane coupling agent solution (the mass ratio of nano-titanium dioxide and silane coupling agent solution was 20:100), and stirred for 5 h by a magnetic stirrer, and then rinsed and filtered with anhydrous ethanol and filter paper, dried in an oven, and ground with a grinder after drying to obtain a modified nanomaterial;

[0063] (3) 3 g of modified nano-titanium dioxide was added to 100 g of vinyl resin (the mass ratio of modified nano-titanium dioxide to vinyl resin was 3:100), and stirred at 2000 r / min for 15 min using a mechanical stirrer. Then, 2 g of methyl ethyl ketone peroxide curing agent, 1 g of cobalt isooctanoate, and 0.5 g of silicone defoaming agent were added (the mass ratio of vinyl resin, curing agent, cobalt isooctanoate, and defoaming agent was 100:2:1:0.5). The mixture was stirred for 15 min and cured at room temperature for 24 h to obtain a modified resin, which was recorded as VES0T3K2.

[0064] Example 2

[0065] (1) 3 g of silane coupling agent KH560 was added to a mixture of 48.5 g of deionized water and 48.5 g of anhydrous ethanol (the mass ratio of deionized water to anhydrous ethanol was 1:1), an appropriate amount of acetic acid was added to adjust the pH value to 4-5, and the mixture was stirred at room temperature with a magnetic stirrer for 30 min to obtain a silane coupling agent solution with a mass concentration of 3%;

[0066] (2) 20g of nano titanium dioxide (particle size 15nm, specific surface area 20-50m 2 / g) and 10g of nano-silicon dioxide (particle size 15nm, specific surface area 220-280m 2 / g) were added into 100 g of silane coupling agent solution (the mass ratio of nano-titanium dioxide and silane coupling agent solution was 20:100, and the mass ratio of nano-silicon dioxide and silane coupling agent solution was 10:100), and stirred for 5 h by a magnetic stirrer, and then rinsed and filtered with anhydrous ethanol and filter paper, dried in an oven, and ground with a grinder after drying to obtain a modified nanomaterial;

[0067] (3) 3 g of modified nano-titanium dioxide and 1 g of modified nano-silica were added to 100 g of vinyl resin (the mass ratio of the total mass of modified nano-titanium dioxide and modified nano-silica to the mass ratio of vinyl resin was 4:100), and stirred at 2000 r / min for 15 min using a mechanical stirrer. Then, 2 g of methyl ethyl ketone peroxide curing agent, 1 g of cobalt isooctanoate and 0.5 g of silicone defoaming agent were added (the mass ratio of vinyl resin, curing agent, cobalt isooctanoate and defoaming agent was 100:2:1:0.5), and stirring was continued for 15 min. The modified resin was cured at room temperature for 24 h to obtain VES1T3K3.

[0068] Example 3

[0069] (1) 2 g of silane coupling agent KH560 was added to a mixture of 49 g of deionized water and 49 g of anhydrous ethanol (the mass ratio of deionized water to anhydrous ethanol was 1:1), an appropriate amount of acetic acid was added to adjust the pH value to 4-5, and the mixture was stirred at room temperature with a magnetic stirrer for 30 min to obtain a silane coupling agent solution with a mass concentration of 2%;

[0070] (2) 20g of nano titanium dioxide (particle size 15nm, specific surface area 20-50m 2 / g) and 10g of nano-silicon dioxide (particle size 15nm, specific surface area 220-280m 2 / g) were added into 100 g of silane coupling agent solution (the mass ratio of nano-titanium dioxide and silane coupling agent solution was 20:100, and the mass ratio of nano-silicon dioxide and silane coupling agent solution was 10:100), and stirred for 5 h by a magnetic stirrer, and then rinsed and filtered with anhydrous ethanol and filter paper, dried in an oven, and ground with a grinder after drying to obtain a modified nanomaterial;

[0071] (3) Add 1 g of modified nano-titanium dioxide and 1 g of modified nano-silica to 50 g of epoxy resin E51 (the mass ratio of the total mass of modified nano-titanium dioxide and modified nano-silica to the mass ratio of epoxy resin E51 is 4:100), add 0.25 g of silicone defoamer (the mass ratio of epoxy resin to defoamer is 0.5:100), use a mechanical stirrer to stir at 2000 r / min for 15 min, then add 50 g of low molecular weight polyamide resin 650 curing agent (the mass ratio of epoxy resin to curing agent is 1:1), continue stirring for 15 min, and cure at room temperature for 24 h to obtain a modified resin, which is recorded as EPS1T1K2.

[0072] Comparative Example 1

[0073] The modified nano-titanium dioxide in Example 1 was omitted, and 2 g of methyl ethyl ketone peroxide curing agent, 1 g of cobalt isooctanoate and 0.5 g of silicone defoamer were added to 100 g of vinyl resin (the mass ratio of vinyl resin, curing agent, cobalt isooctanoate and defoamer was 100:2:1:0.5), stirred for 15 min, and cured at room temperature for 24 h to obtain a vinyl resin, which was recorded as VES0TOK0.

[0074] Comparative Example 2

[0075] The modified nano-titanium dioxide and modified nano-silicon dioxide in Example 3 were omitted, and 50 g of low molecular weight polyamide resin 650 curing agent was added to 50 g of epoxy resin E51 (the mass ratio of epoxy resin to curing agent was 1:1), stirred for 15 min, and cured at room temperature for 24 h to obtain a modified resin, which was recorded as EPS0T0K0.

[0076] Comparative Example 3

[0077] 3 g of nano-titanium dioxide and 3 g of nano-silicon dioxide were added to 50 g of epoxy resin E51 (the mass ratio of the total mass of nano-titanium dioxide and nano-silicon dioxide to the epoxy resin E51 was 6:100), and stirred at 2000 r / min for 15 min using a mechanical stirrer. 0.25 g of silicone defoamer was added (the mass ratio of epoxy resin to defoamer was 0.5:100), and then 50 g of low molecular weight polyamide resin 650 curing agent was added (the mass ratio of epoxy resin to curing agent was 1:1). Stirring was continued for 15 min, and the modified resin was cured at room temperature for 24 h to obtain the modified resin, which was recorded as EPS3T3K0.

[0078] Tensile tests were conducted on the resin matrices prepared in Examples 1 and 2, and Comparative Example 1, and their tensile stress-strain curves are shown in Figure 2. Tensile tests were conducted on the resin matrices prepared in Example 3 and Comparative Examples 2-3, and their tensile stress-strain curves are shown in Figure 3. As can be seen from Figures 2 and 3, the tensile strength of the modified cast resin bodies was not significantly improved, but the ultimate strain was increased, and the ductility was greatly improved. The data in the lower part of the figure represents the ultimate strain of the corresponding sample; the data in the upper part of the figure represents the area enclosed by the stress-strain curve of the corresponding sample. The area enclosed by the stress-strain curve represents the tensile toughness of the resin, and it was found that the toughness of the cast resin bodies was significantly increased. The toughness of the epoxy resin increased by 95%, and the ductility increased by 99%. The toughness of the vinyl resin increased by 364%, and the ductility increased by 345%, solving the problem of the brittleness of the resin matrix.

[0079] The description of the above embodiments is only intended to help understand the method of the present invention and its core concept. It should be noted that for those skilled in the art, without departing from the principles of the present invention, several improvements and modifications may be made to the present invention, and these improvements and modifications also fall within the scope of protection of the claims of the present invention. Various modifications to these embodiments are obvious to those skilled in the art, and the general principles defined herein may be implemented in other embodiments without departing from the spirit or scope of the present invention. Therefore, the present invention will not be limited to the embodiments shown herein, but will conform to the widest scope consistent with the principles and novel features disclosed herein.

Claims

1. A method for preparing a silane coupling agent solution-modified nanomaterial toughened resin matrix, comprising the following steps: (1) mixing a silane coupling agent KH560, ethanol, water and acetic acid for hydrolysis reaction to obtain a silane coupling agent solution; (2) mixing the silane coupling agent solution obtained in step (1) with the nanomaterial to perform a modification treatment to obtain a modified nanomaterial; (3) The modified nanomaterial obtained in step (2) is mixed with a resin and a curing agent and then cured to obtain a silane coupling agent solution-modified nanomaterial toughened resin matrix.

2. The preparation method according to claim 1, characterized in that: The mass concentration of the silane coupling agent solution in step (1) is 2-4%.

3. The preparation method according to claim 1, characterized in that: The mass ratio of ethanol to water in the step (1) is 1:(0.5-1.5).

4. The preparation method according to claim 1, characterized in that: The pH value of the silane coupling agent solution in step (1) is 4-6.

5. The preparation method according to claim 1, characterized in that: The nanomaterial in step (2) includes one or more of nano titanium dioxide and nano silicon dioxide.

6. The preparation method according to claim 1 or 5, characterized in that: The particle size of the nanomaterial in step (2) is 10 to 20 nm.

7. The preparation method according to claim 5, characterized in that: The specific surface area of ​​the nano titanium dioxide is 20 to 50 m 2 / g.

8. The preparation method according to claim 5, characterized in that: The specific surface area of ​​the nano-silicon dioxide is preferably 220 to 280 m 2 / g.

9. The preparation method according to claim 1 or 2, characterized in that: In the step (2), the mass ratio of the nano material to the silane coupling agent solution is (5-20):

100.

10. The preparation method according to claim 1, characterized in that: The modification treatment time in step (2) is 3 to 6 hours.

11. The preparation method according to claim 1, characterized in that: In the step (3), the mass ratio of the modified nanomaterial to the resin is (1-5):

100.

12. The preparation method according to claim 1, characterized in that: The resin in step (3) includes epoxy resin or vinyl resin.

13. The preparation method according to claim 1, characterized in that: The curing temperature in step (3) is 20 to 30° C., and the curing time is 12 to 36 hours.

14. A resin matrix toughened by nanomaterials modified by a silane coupling agent solution prepared by the preparation method according to any one of claims 1 to 13.

15. Use of the silane coupling agent solution modified nanomaterials as claimed in claim 14 to toughen resin matrix in resin-based composite materials.

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