Preparation and application of epoxy / MOF composite material

Abstract

The invention discloses preparation and application of an epoxy / MOF composite material, and belongs to the technical field of preparation of organic and inorganic composites.The preparation method comprises the steps that 1, after imidazole alcohol, epoxy chloropropane and tetrabutylammonium bromide are evenly mixed, caustic soda flakes are added, a reaction is conducted at a certain temperature, and then filtering and washing are conducted; and (2) adding a metal ion solution into the product in the step (1), reacting for a period of time at a certain temperature, filtering, washing with water, and drying to obtain the epoxy / MOF composite material. The method has the beneficial effects that the ring-closure reaction is carried out under the action of caustic soda flakes and tetrabutylammonium bromide as a phase transfer catalyst to generate epoxy glycidyl ether with an imidazole structure. When used as an epoxy resin additive, the epoxy resin additive enhances the compatibility with epoxy resin, improves the dispersibility of powder in epoxy resin, greatly enhances the heat resistance of epoxy resin, and avoids the defects of agglomeration and non-uniform dispersion of a composite material in epoxy resin.

Description

Technical field:

[0001] The invention belongs to the technical field of preparation of organic and inorganic composite materials, and specifically relates to the preparation of an epoxy / MOF composite material and the application of a heat-resistant agent. Background technology:

[0002] Epoxy resin is a type of thermosetting resin, which is widely used in adhesives, coatings and other fields. Epoxy resin is composed of epoxy resin polymer, curing agent, filler and various additives. After curing, it has high hardness, high strength, acid and alkali resistance and good mechanical properties. With the improvement of scientific and technological level, higher requirements are put forward for the heat resistance of epoxy resin in aerospace, new energy and other industries. In air atmosphere, epoxy resin generally undergoes thermal oxidation decomposition at about 200°C.

[0003] At present, improving the heat resistance of epoxy resin is mainly achieved by changing the structure and composition of the polymer, modifying the curing agent and adding heat-resistant additives. The invention patent (CN201910884583.1) discloses a bifunctional epoxy resin-silicone rubber block interpenetrating network material with improved heat resistance, and the system can maintain long-term stability. The patent uses epoxy resin and high-temperature resistant silicone polymers to copolymerize to improve the heat resistance of epoxy resin. The invention patent (CN202410150760.4) improves the heat resistance temperature of epoxy resin by multi-site non-covalent cross-linking, and adds cage-type polysilsesquioxane with multiple cross-linking sites to the epoxy resin material. The invention patent (CN200680007911.0) improves the flame retardancy and heat resistance of epoxy resin by using phosphorus-modified epoxy resin and phosphazene compounds as flame retardant additives as additives to epoxy resin. The invention patent (CN202311173521.2) prepared a heat-resistant toughening agent for epoxy resin, which was prepared by encapsulating the surface of silicone resin with carbon-based polymers through a platinum-catalyzed addition reaction of epoxy monomers containing C=C and hydrogen-containing silicone resins. However, as a heat-resistant additive for epoxy resin, it is necessary to perform surface epoxy modification to increase compatibility with epoxy resin and reduce the occurrence of phase separation.

[0004] Metal organic complexes MOFs are a type of organic / inorganic hybrid porous materials formed by self-assembly of metal ions or metal clusters and organic ligands. MOFs can be used as epoxy resin curing agents in epoxy resin systems. For example, the invention patent (CN202211574974.1) announced a new type of bifunctional epoxy resin latent curing agent (P-ILs@ZIF-8 epoxy resin curing agent). Compared with traditional curing agents, its low-temperature curing property and storage stability at room temperature have been greatly improved, and the curing effect is better. In addition, due to the introduction of phosphorus-containing ionic liquids in the curing agent, the modified epoxy resin will have certain flame retardancy. In order to solve the process defect of difficult dispersion of nanoparticles in conventional hybrid epoxy adhesives with inorganic components, the invention patent (CN202310249701.8) discloses a MOF-modified epoxy resin, including the following raw material components: tetraethyl orthosilicate, γ-(2,3-epoxypropoxy)propyltrimethoxysilane, 2-methylimidazole, isopropanol, Zn(NO3)2·6H2O, epoxy resin, and dibutyltin dilaurate.

[0005] At present, it is still a huge challenge to enhance the compatibility of additives with epoxy resins and obtain epoxy resins with high heat resistance through the design of new structures. Summary of the invention:

[0006] In order to solve the above problems and overcome the shortcomings of the prior art, the present invention provides a preparation and application of an epoxy / MOF composite material, which can effectively solve the compatibility with epoxy resin and obtain epoxy resin with high heat resistance.

[0007] The specific technical solution of the present invention to solve the above technical problems is: 1. A method for preparing an epoxy / MOF composite material, characterized by comprising the following steps:

[0008] (1) After uniformly mixing imidazoline, epichlorohydrin and tetrabutylammonium bromide, adding caustic soda flakes and reacting at a certain temperature, filtering and washing;

[0009] (2) Adding a metal ion solution to the product in (1), reacting the mixture at a certain temperature for a period of time, filtering the mixture, washing the mixture with water, and drying the mixture to obtain an epoxy / MOF composite material.

[0010] Furthermore, in step (1), the imidazoline alcohol is 1-(2-hydroxyethyl)imidazole or imidazoleethanol.

[0011] Furthermore, in step (1), the molar ratio of imidazole alcohol:epichlorohydrin:tetrabutylammonium bromide:catechol is 1:(3-6):(0.01-0.03):(1-2).

[0012] Furthermore, in step (1), the reaction temperature is 30-50°C and the reaction time is 2-6h.

[0013] Furthermore, in step (1), the washing liquid is any one of epichlorohydrin, ethanol and toluene.

[0014] Furthermore, in step (2), the metal ion solution is any one of tin, zinc, cerium, and iron ions.

[0015] Furthermore, in step (2), the concentration of the metal ion solution is 0.5 mol / L, and the molar ratio of imidazole:metal ion is 1:(0.5-1).

[0016] Furthermore, in step (2), the reaction temperature is 60-90° C. and the reaction time is 1-4 h.

[0017] Furthermore, in step (2), the drying temperature is 90-120°C.

[0018] The epoxy / MOF composite material is prepared by the preparation method of the epoxy / MOF composite material, and the epoxy / MOF composite material is used as a heat-resistant agent for epoxy resin; the structural formula of the epoxy / MOF composite material is:

[0019]

[0020] The beneficial effects of the present invention are:

[0021] The present invention uses tetrabutylammonium bromide as a phase transfer catalyst and caustic soda to perform a ring-closing reaction to generate epoxy glycidyl ether with an imidazole structure. When used as an additive for epoxy resin, the compatibility with the epoxy resin is enhanced, the dispersibility of the powder in the epoxy resin is improved, the heat resistance of the epoxy resin is greatly improved, and the shortcomings of agglomeration and uneven dispersion of the composite material in the epoxy resin are avoided. The technical process of the present invention has high controllability, excellent product performance, and is suitable for large-scale production. Description of the drawings:

[0022] Attached Figure 1 is the infrared spectrum of the epoxy / MOF composite material prepared by the present invention;

[0023] Attached Figure 2 is a scanning electron microscope image of the epoxy / MOF composite material prepared by the present invention;

[0024] Attached Figure 3 This is a state diagram of epoxy / MOF composite material prepared by the present invention after adding epoxy resin;

[0025] Attached Figure 4 This is a state diagram of the epoxy / MOF composite material prepared in Comparative Example 2 after epoxy resin is added;

[0026] Attached Figure 5 It is the thermogravimetric spectrum of pure epoxy resin of epoxy / MOF composite material prepared by the present invention; Specific implementation method:

[0027] In the description of the present invention, specific details are only for a full understanding of the embodiments of the present invention, but those skilled in the art should know that the implementation of the present invention is not limited to these details. In addition, well-known structures and functions are not described or shown in detail to avoid blurring the key points of the embodiments of the present invention. For those of ordinary skill in the art, the specific meanings of the above terms in the present invention can be understood according to specific circumstances.

[0028] Specific implementation of the present invention:

[0029] In order to better understand the present invention, a specific embodiment is used for illustration. It is worth emphasizing that the effect of this embodiment is not substantially different from the various embodiments within the protection scope of the present invention, including the respective reagents and the content ratio of the reagents, and all of them can achieve the effects described in the present invention and solve the above-mentioned problems. Other combinations are not described here.

[0030] Embodiment 1:

[0031] (1) Take 0.1 mol of 1-(2-hydroxyethyl)imidazole, 0.4 mol of epichlorohydrin, and 0.0015 mol of tetrabutylammonium bromide, add 0.15 mol of flake caustic soda in batches under magnetic stirring at 38°C until the raw materials react completely, filter, wash the filter cake twice with epichlorohydrin, transfer the filtrate to a rotary evaporator to evaporate the solvent under reduced pressure, and obtain a viscous liquid.

[0032] (2) Add 120 mL of a 0.5 mol / L stannous chloride aqueous solution to the above viscous liquid, reflux at 75° C. for 2.5 h under stirring, cool and filter, wash the filter cake twice with pure water, transfer to an oven at 105° C. and dry to constant weight to obtain a solid powder.

[0033] (3) Add 5% of the above solid powder into epoxy resin for curing.

[0034] Embodiment 2:

[0035] (1) Take 0.1 mol of imidazole ethanol, 0.5 mol of epichlorohydrin, and 0.002 mol of tetrabutylammonium bromide, add 0.15 mol of flake caustic soda in batches under magnetic stirring at 40°C and keep warm until the raw materials are completely reacted, filter, wash the filter cake twice with ethanol, transfer the filtrate to a rotary evaporator to evaporate the solvent under reduced pressure, and obtain a viscous liquid.

[0036] (2) Add 120 mL of a 0.5 mol / L stannous chloride aqueous solution to the above viscous liquid, reflux at 80° C. for 2 h under stirring, cool and filter, wash the filter cake twice with pure water, transfer to an oven at 120° C. and dry to constant weight to obtain a solid powder.

[0037] (3) Add 5% of the above solid powder into epoxy resin for curing.

[0038] Embodiment 3:

[0039] (1) Take 0.1 mol of 1-(2-hydroxyethyl)imidazole, 0.4 mol of epichlorohydrin, and 0.0025 mol of tetrabutylammonium bromide, add 0.2 mol of flake caustic soda in batches under magnetic stirring at 30°C and keep warm until the raw materials are completely reacted, filter, wash the filter cake twice with toluene, transfer the filtrate to a rotary evaporator to evaporate the solvent under reduced pressure, and obtain a viscous liquid.

[0040] (2) Add 120 mL of 0.5 mol / L zinc chloride aqueous solution to the above viscous liquid, reflux at 75° C. for 3 h under stirring, cool and filter, wash the filter cake twice with pure water, transfer to an oven at 90° C. and dry to constant weight to obtain a solid powder.

[0041] (3) Add 5% of the above solid powder into epoxy resin for curing.

[0042] Embodiment 4:

[0043] (1) Take 0.1 mol of 1-(2-hydroxyethyl)imidazole, 0.6 mol of epichlorohydrin, and 0.003 mol of tetrabutylammonium bromide, add 0.2 mol of flake caustic soda in batches under magnetic stirring at 30°C and keep warm until the raw materials are completely reacted, filter, wash the filter cake twice with toluene, transfer the filtrate to a rotary evaporator to evaporate the solvent under reduced pressure, and obtain a viscous liquid.

[0044] (2) Add 200 mL of a 0.5 mol / L aqueous solution of cerium nitrate to the above viscous liquid, reflux at 90° C. for 1 h under stirring, cool and filter, wash the filter cake twice with pure water, transfer to an oven at 120° C. and dry to constant weight to obtain a solid powder.

[0045] (3) Add 5% of the above solid powder into epoxy resin for curing.

[0046] Embodiment 5:

[0047] (1) Take 0.1 mol of imidazole ethanol, 0.3 mol of epichlorohydrin, and 0.001 mol of tetrabutylammonium bromide, add 0.10 mol of flake caustic soda in batches under magnetic stirring at 40°C and keep warm until the raw materials are completely reacted, filter, wash the filter cake twice with epichlorohydrin, transfer the filtrate to a rotary evaporator to evaporate the solvent under reduced pressure, and obtain a viscous liquid.

[0048] (2) Add 100 mL of 0.5 mol / L ferric chloride aqueous solution to the above viscous liquid, reflux at 80° C. for 3 h under stirring, cool and filter, wash the filter cake twice with pure water, transfer to an oven at 110° C. and dry to constant weight to obtain a solid powder.

[0049] (3) Add 5% of the above solid powder into epoxy resin for curing.

[0050] Embodiment 6:

[0051] (1) Take 0.1 mol of imidazole ethanol, 0.6 mol of epichlorohydrin, and 0.003 mol of tetrabutylammonium bromide, add 0.20 mol of flake caustic soda in batches under magnetic stirring at 35°C and keep warm until the raw materials are completely reacted, filter, wash the filter cake twice with epichlorohydrin, transfer the filtrate to a rotary evaporator to evaporate the solvent under reduced pressure, and obtain a viscous liquid.

[0052] (2) Add 200 mL of a 0.5 mol / L aqueous solution of cerium nitrate to the above viscous liquid, reflux at 80° C. for 1 h under stirring, cool and filter, wash the filter cake twice with pure water, transfer to an oven at 120° C. and dry to constant weight to obtain a solid powder.

[0053] (3) Add 5% of the above solid powder into epoxy resin for curing.

[0054] Embodiment 7:

[0055] (1) Take 0.1 mol of imidazole ethanol, 0.5 mol of epichlorohydrin, and 0.003 mol of tetrabutylammonium bromide, add 0.20 mol of flake caustic soda in batches under magnetic stirring at 35°C and keep warm until the raw materials are completely reacted, filter, wash the filter cake twice with epichlorohydrin, transfer the filtrate to a rotary evaporator to evaporate the solvent under reduced pressure, and obtain a viscous liquid.

[0056] (2) Add 200 mL of 0.5 mol / L zinc chloride aqueous solution to the above viscous liquid, reflux at 60° C. for 4 h under stirring, cool and filter, wash the filter cake twice with pure water, transfer to an oven at 100° C. and dry to constant weight to obtain a solid powder.

[0057] (3) Add 5% of the above solid powder into epoxy resin for curing.

[0058] Embodiment 8:

[0059] (1) Take 0.1 mol of 1-(2-hydroxyethyl)imidazole, 0.4 mol of epichlorohydrin, and 0.0015 mol of tetrabutylammonium bromide, add 0.15 mol of flake caustic soda in batches under magnetic stirring at 38°C until the raw materials react completely, filter, wash the filter cake with ethanol three times, transfer the filtrate to a rotary evaporator to evaporate the solvent under reduced pressure, and obtain a viscous liquid.

[0060] (2) Add 120 mL of a 0.5 mol / L stannous chloride aqueous solution to the above viscous liquid, reflux at 75° C. for 2.5 h under stirring, cool and filter, wash the filter cake twice with pure water, transfer to an oven at 105° C. and dry to constant weight to obtain a solid powder.

[0061] (3) Add 5% of the above solid powder into epoxy resin for curing.

[0062] In order to more intuitively demonstrate the process advantages of the present invention, the preparation method of the epoxy / MOF composite material of the present invention is compared with the method of equivalent replacement using the same process.

[0063] Comparative Example 1: Same as Example 1, except that there is no metal ion;

[0064] (1) Take 0.1 mol of 1-(2-hydroxyethyl)imidazole, 0.4 mol of epichlorohydrin, and 0.0015 mol of tetrabutylammonium bromide, add 0.15 mol of flake caustic soda in batches under magnetic stirring at 38°C until the raw materials react completely, filter, wash the filter cake with ethanol three times, transfer the filtrate to a rotary evaporator to evaporate the solvent under reduced pressure, and obtain a viscous liquid.

[0065] (2) Add 5% of the above viscous liquid into epoxy resin for curing.

[0066] Comparative Example 2: Same as Example 1, except that there is no phase transfer catalyst;

[0067] (1) Take 0.1 mol of 1-(2-hydroxyethyl)imidazole and 0.4 mol of epichlorohydrin, add 0.15 mol of flake caustic soda in batches under magnetic stirring at 38°C and keep warm until the raw materials are completely reacted, filter, wash the filter cake twice with epichlorohydrin, transfer the filtrate to a rotary evaporator and evaporate the solvent under reduced pressure to obtain a viscous liquid.

[0068] (2) Add 120 mL of a 0.5 mol / L stannous chloride aqueous solution to the above viscous liquid, reflux at 75° C. for 2.5 h under stirring, cool and filter, wash the filter cake twice with pure water, transfer to an oven at 105° C. and dry to constant weight to obtain a solid powder.

[0069] (3) Add 5% of the above solid powder into epoxy resin for curing.

[0070] Comparative Example 3: Same as Example 1, except that the phase transfer catalyst is replaced with butyltriphenylphosphonium bromide;

[0071] (1) Take 0.1 mol of 1-(2-hydroxyethyl)imidazole, 0.4 mol of epichlorohydrin, and 0.0015 mol of butyltriphenylphosphonium bromide, add 0.15 mol of flake caustic soda in batches under magnetic stirring at 38°C until the raw materials react completely, filter, wash the filter cake twice with epichlorohydrin, transfer the filtrate to a rotary evaporator to evaporate the solvent under reduced pressure, and obtain a viscous liquid.

[0072] (2) Add 120 mL of a 0.5 mol / L stannous chloride aqueous solution to the above viscous liquid, reflux at 75° C. for 2.5 h under stirring, cool and filter, wash the filter cake twice with pure water, transfer to an oven at 105° C. and dry to constant weight to obtain a solid powder.

[0073] (3) Add 5% of the above solid powder into epoxy resin for curing.

[0074] Comparative Example 4: Same as Example 1, except that stannous chloride is replaced by calcium chloride;

[0075] (1) Take 0.1 mol of 1-(2-hydroxyethyl)imidazole, 0.4 mol of epichlorohydrin, and 0.0015 mol of tetrabutylammonium bromide, add 0.15 mol of flake caustic soda in batches under magnetic stirring at 38°C and keep warm until the raw materials are completely reacted, filter, wash the filter cake twice with epichlorohydrin, transfer the filtrate to a rotary evaporator to evaporate the solvent under reduced pressure, and obtain a viscous liquid.

[0076] (2) Add 120 mL of 0.5 mol / L calcium chloride aqueous solution to the above viscous liquid, reflux at 75°C for 2.5 h with stirring, cool and filter, wash the filter cake twice with pure water, transfer to an oven at 105°C and dry to constant weight to obtain a solid powder.

[0077] (3) Add 5% of the above solid powder into epoxy resin for curing.

[0078] The above examples and comparative examples were added into epoxy resin, and the thermal weight loss was measured at 300°C.

[0079] Table 1: Comparison of dispersibility and thermal weight loss performance of different embodiments and comparative examples:

[0080]

[0081] From the data analysis in Table 1, we can see that:

[0082] (1) The experimental data of Examples 1-8 show that there is no significant difference between the various examples.

[0083] Taking Example 1 as an example: the infrared spectrum of the product in step (1) is as follows Figure 1As shown in the figure, characteristic peaks of imidazole (1570 cm-1 for vibration of imidazole ring skeleton) and epoxy (1150 cm-1 for epoxy group) appeared in the spectrum, indicating that the product has both functional groups. The scanning electron microscope of the solid powder in step (2) Figure 2 The product is in the form of granules. The cured product is characterized by thermogravimetric properties under the test conditions of 100-800°C and a heating rate of 10°C / min. The heat resistance of the product is evaluated by thermogravimetric analysis. Figure 3 After the product of Example 1 is added to the epoxy resin, it can be evenly dispersed therein without particle agglomeration. Figure 4 compared to, Figure 4 There is agglomeration phenomenon in the

[0084] Figure 5 The thermogravimetric spectra of pure epoxy resin and the product of Example 1 are shown. It can be seen that the epoxy resin with the product of Example 1 has a thermal weight loss of 14% at 300°C, while the pure epoxy resin has a thermal weight loss of 20% at 300°C. After adding the product of Example 1, the thermal decomposition temperature and heat resistance of the epoxy resin are significantly improved. The product of Example 1 participates in the reaction during the curing process of the epoxy resin and forms a good dispersion in the epoxy resin. The contact area between the two is greatly increased, which effectively improves its heat resistance.

[0085] This may be because in the preparation method of the epoxy / MOF composite material described in the present invention, the hydroxyl group of imidazole alcohol is first reacted with the epoxy group of epichlorohydrin, and a closed-ring reaction is carried out under the action of tetrabutylammonium bromide as a phase transfer catalyst and caustic soda to generate epoxy glycidyl ether with an imidazole structure. The imidazole epoxy glycidyl ether is reacted with metal ions in an aqueous phase to generate a MOF structure, and the MOF is in situ grown in the epoxy glycidyl ether structure, and the outer surface of the MOF is an epoxy group. The composite material of MOF / epoxy glycidyl ether has both a metal organic complex structure and an epoxy structure. When used as an additive for epoxy resin, it enhances the compatibility with epoxy resin, improves the dispersibility of the powder in the epoxy resin, and greatly improves the heat resistance of the epoxy resin.

[0086] (2) The experimental data of Comparative Examples 1 and 4 show that:

[0087] Comparative Example 1 is the same as Example 1 except that it does not contain metal ions. The thermogravimetric results show that when the product of Comparative Example 1 is added to epoxy resin, the thermal weight loss at 300° C. is 20%.

[0088] This is much higher than 14% of the present invention, which indicates that the addition of metal ions can have a certain effect on the thermal weight loss performance of the composite material in the epoxy resin, especially when the metal ion solution is tin, zinc, cerium, or iron ions, it can have a positive effect on the thermal weight loss performance of the composite material in the epoxy resin;

[0089] In combination with Comparative Example 4, the difference between Comparative Example 4 and Example 1 is that the difference is calcium chloride. According to the thermogravimetric results, the product of Comparative Example 4 is added to the epoxy resin, and the thermal weight loss at 300°C is 19%;

[0090] From this, it can be seen that not all metal ions have a positive effect on the thermal weight loss properties of composite materials in epoxy resin;

[0091] (3) The experimental data of Comparative Example 2 show that:

[0092] Since Comparative Example 2 is the same as Example 1 except that there is no phase transfer catalyst, no product can be obtained without a phase transfer catalyst, the reaction is too slow, and there is almost no reaction, so it is not worth studying.

[0093] (4) The experimental data of Comparative Example 3 show that:

[0094] Compared with Example 1, the difference in Comparative Example 3 is that the phase transfer catalyst is replaced with butyl triphenyl phosphonium bromide. The catalytic performance of butyl triphenyl phosphonium bromide in this system is lower than that of tetrabutyl ammonium bromide, and the thermal weight loss of the product in epoxy resin at 300° C. is 18%. In addition, butyl triphenyl phosphonium bromide is expensive, resulting in excessively high product costs and no industrial prospects.

[0095] In summary:

[0096] The present invention uses tetrabutylammonium bromide as a phase transfer catalyst and caustic soda to perform a ring-closing reaction to generate epoxy glycidyl ether with an imidazole structure. When used as an additive for epoxy resin, the compatibility with the epoxy resin is enhanced, the dispersibility of the powder in the epoxy resin is improved, the heat resistance of the epoxy resin is greatly improved, and the shortcomings of agglomeration and uneven dispersion of the composite material in the epoxy resin are avoided. The technical process of the present invention has high controllability, excellent product performance, and is suitable for large-scale production.

[0097] The epoxy / MOF composite material of the present invention has a positive effect on improving the heat resistance of epoxy resin, and the mixture has no particles and agglomerates, and the two have good compatibility. The process is controllable and suitable for large-scale production.

Claims

1. A method for preparing an epoxy / MOF composite material, characterized in that The following steps are involved: (1) After uniformly mixing imidazoline, epichlorohydrin and tetrabutylammonium bromide, adding caustic soda flakes and reacting at a certain temperature, filtering and washing; (2) Adding a metal ion solution to the product in (1), reacting the mixture at a certain temperature for a period of time, filtering the mixture, washing the mixture with water, and drying the mixture to obtain an epoxy / MOF composite material.

2. The method for preparing the epoxy / MOF composite material according to claim 1, characterized in that In step (1), the imidazole alcohol is 1-(2-hydroxyethyl)imidazole or imidazoleethanol.

3. The method for preparing the epoxy / MOF composite material according to claim 1, characterized in that In step (1), the molar ratio of imidazole alcohol:epichlorohydrin:tetrabutylammonium bromide:catechol is 1:(3-6):(0.01-0.03):(1-2).

4. The method for preparing the epoxy / MOF composite material according to claim 1, characterized in that In step (1), the reaction temperature is 30-50°C and the reaction time is 2-6h.

5. The method for preparing the epoxy / MOF composite material according to claim 1, characterized in that In step (1), the washing liquid is any one of epichlorohydrin, ethanol and toluene.

6. The method for preparing the epoxy / MOF composite material according to claim 1, characterized in that In step (2), the metal ion solution is any one of tin, zinc, cerium and iron ions.

7. The method for preparing the epoxy / MOF composite material according to claim 1, characterized in that In step (2), the concentration of the metal ion solution is 0.5 mol / L, and the molar ratio of imidazole:metal ion is 1:(0.5-1).

8. The method for preparing the epoxy / MOF composite material according to claim 1, characterized in that In step (2), the reaction temperature is 60-90° C. and the reaction time is 1-4 h.

9. The method for preparing the epoxy / MOF composite material according to claim 1, characterized in that In step (2), the drying temperature is 90-120°C.

10. An epoxy / MOF composite material prepared by the preparation method of an epoxy / MOF composite material according to any one of claims 1 to 9, wherein the epoxy / MOF composite material is characterized in that Used as heat resistant agent for epoxy resin; the structural formula of epoxy / MOF composite material is:

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