Epoxy resin cement and preparation method thereof

Abstract

The present invention relates to the technical field of epoxy resin cement, and in particular to an epoxy resin cement and a preparation method thereof. The epoxy resin cement comprises a component A and a component B, wherein the mass ratio of the component A to the component B is 1: (0.5-1.5); in terms of mass percentage, the component A is composed of the following raw materials: 8%-40% of a bio-based epoxy resin monomer, 52-84% of an epoxy resin, and a diluent balance; in terms of mass percentage, the component B is composed of the following raw materials: 88-94.4% of a curing agent, 0.5-3% of an accelerator, 5-8% of an inorganic filler, and a tin-containing Schiff base-modified carbon nanotube balance. The epoxy resin cement has excellent mechanical properties and anti-photooxidation properties.

Description

Technical Field

[0001] The invention relates to the technical field of epoxy resin putty, and in particular to epoxy resin putty and a preparation method thereof. Background Art

[0002] The transformer is one of the most important electrical equipment in the power system, but transformer oil leakage occurs from time to time. Severe leakage not only reduces the service life of the transformer, but also may have a significant impact on the long-term safe and stable operation of the power plant. At present, the sealing method for transformer insulating oil leakage is usually adhesive patching.

[0003] Epoxy resin is a high-performance thermosetting resin. It is widely used in the adhesive field because of its good mechanical properties, chemical resistance, water resistance, low dimensional shrinkage and high electrical insulation. At present, the main component of epoxy resin putty on the market is mostly bisphenol A epoxy resin (DGEBA). The cross-linked network formed after curing of this epoxy resin gives it excellent strength and temperature resistance, but its impact resistance and weather resistance are poor, especially its resistance to ultraviolet sunlight. However, the transformer is exposed to the outdoors for a long time, and there are electromagnetic vibrations during operation. The flexibility, mechanical strength and photooxidation resistance of the epoxy resin putty are high, so it is necessary to modify the epoxy resin putty.

[0004] Chelidonic acid, a natural product derived from chelidonium, has two natural meta-substitution sites, which are easily epoxidized. The document "Tin-Naphthalene Sulfonic Acid Complexes as Photostabilizers for Poly(vinyl chloride)" (Molecules 26.12 (2021): 3629) records that organotin complexes have the function of light stabilizers.

[0005] Based on the above background technology, the present invention uses chelidonic acid to prepare a bio-based epoxy resin monomer, blends it with bisphenol A epoxy resin, and uses tin-containing Schiff base-modified carbon nanotubes as anti-photooxidants to successfully prepare an epoxy adhesive with excellent antioxidant and mechanical properties, which is expected to be used in transformer oil leakage sealing. Summary of the invention

[0006] In order to overcome the deficiencies of the prior art, one of the objects of the present invention is to provide an epoxy resin putty having excellent anti-oxidation and mechanical properties.

[0007] The second object of the present invention is to provide a method for preparing epoxy resin putty, and the preparation process is simple.

[0008] One of the purposes of the present invention is achieved by the following technical solution:

[0009] An epoxy resin putty, comprising a component A and a component B, wherein the mass ratio of the component A to the component B is 1:(0.5-1.5); the component A is composed of the following raw materials in terms of mass percentage: 8%-40% of a bio-based epoxy resin monomer, 52-84% of an epoxy resin, and the balance of a diluent; the component B is composed of the following raw materials in terms of mass percentage: 88-94.4% of a curing agent, 0.5-3% of an accelerator, 5-8% of an inorganic filler, and the balance of tin-containing Schiff base-modified carbon nanotubes.

[0010] Furthermore, the preparation process of the bio-based epoxy resin monomer is as follows:

[0011]

[0012] (1) adding chelidonic acid, allyl bromide and triethylamine to a mixed solution of dimethyl sulfoxide and acetone for heating and stirring to react, and purifying after the reaction to obtain intermediate 1;

[0013] (2) The intermediate 1 of step (1) and m-chloroperbenzoic acid are added to dichloromethane for reaction. After the reaction is completed, the monomer is purified to obtain a bio-based epoxy resin monomer.

[0014] Furthermore, in step (1), the molar ratio of chelidonic acid, allyl bromide and triethylamine is 1:(3.5-4):(2-2.5); the temperature of the heating and stirring reaction is 190-200°C, and the heating and stirring reaction time is 24-30h; and the volume ratio of dimethyl sulfoxide and acetone is 1:1.

[0015] Furthermore, in step (2), the molar ratio of the intermediate 1 to m-chloroperbenzoic acid is 1:(2.5-3), the reaction temperature is 35-45° C., and the reaction time is 2.5-3.5 days.

[0016] Furthermore, the preparation process of the tin-containing Schiff base modified carbon nanotubes is as follows:

[0017]

[0018] (a) dispersing the aminated carbon nanotubes in chloroform, then adding 2-hydroxy-1-naphthaldehyde to react, and drying after the reaction to obtain Schiff base modified carbon nanotubes;

[0019] (b) The Schiff base-modified carbon nanotubes and triphenyltin chloride prepared in step (a) are added to chloroform for ultrasonic treatment, and then dried to obtain tin-containing Schiff base-modified carbon nanotubes.

[0020] Furthermore, in step (a), the mass ratio of the amino carbon nanotubes to 2-hydroxy-1-naphthaldehyde is 1:(1.8-4.8), the reaction temperature is 55-65° C., and the reaction time is 2.5-3.5 h.

[0021] Furthermore, in step (b), the mass ratio of the Schiff base modified carbon nanotubes to triphenyltin chloride is 1:(0.25-0.6), and the ultrasonic treatment time is 0.5-1.5h.

[0022] Furthermore, the epoxy resin is bisphenol A epoxy resin; the diluent is ethylene glycol glycidyl ether; the curing agent is alicyclic amine modified epoxy curing agent; the accelerator is 2,4,6-tris(dimethylaminomethyl)phenol; and the inorganic filler is silicon micropowder.

[0023] The second object of the present invention is achieved by adopting the following technical solution:

[0024] The preparation method of the above-mentioned epoxy resin putty comprises the following steps:

[0025] I. Preparation of component A: According to the mass percentage, the bio-based epoxy resin monomer, epoxy resin and diluent are mixed, stirred evenly, and subjected to high-speed dispersion and vacuum degassing to obtain component A;

[0026] II. Preparation of component B: According to the mass percentage, the curing agent, the accelerator, the inorganic filler and the tin-containing Schiff base-modified carbon nanotubes are mixed and stirred uniformly, and the component B is obtained by high-speed dispersion and vacuum degassing;

[0027] III. Preparation of epoxy resin putty: According to the mass ratio, component A and component B are mixed evenly, and after curing at room temperature, epoxy resin putty is obtained.

[0028] Furthermore, in steps I and II, the time for high-speed dispersion is 20-40 minutes, and the time for curing is 20-30 minutes.

[0029] Compared with the prior art, the present invention has the following beneficial effects:

[0030] The epoxy resin putty of the present invention adds raw materials such as bio-based epoxy resin monomers and tin-containing Schiff base modified carbon nanotubes, thereby improving the mechanical properties and light oxidation resistance of the epoxy resin putty. The bio-based epoxy resin monomer is synthesized using chelidonic acid, and the epoxide value of the monomer is relatively high. The bio-based epoxy resin monomer is blended and modified with epoxy resin to improve the crosslinking density of the epoxy resin putty, thereby improving its mechanical strength. In addition, flexible groups such as ether bonds and ester groups are introduced into the bio-based epoxy resin monomer, which can improve the flexibility of the epoxy resin putty. The triphenyltin chloride loaded on the carbon nanotubes in the tin-containing Schiff base modified carbon nanotubes can act together with the Schiff base as an organic tin complex to improve the light oxidation resistance of the epoxy resin putty. BRIEF DESCRIPTION OF THE DRAWINGS

[0031] Figure 1 This is a graph showing the nuclear magnetic resonance characterization results of the bio-based epoxy resin monomer prepared in Example 1 of the present invention. DETAILED DESCRIPTION

[0032] The present invention is further described below in conjunction with the accompanying drawings and specific embodiments. It should be noted that, under the premise of no conflict, the embodiments described below or the technical features can be arbitrarily combined to form new embodiments. The specific conditions not specified in the embodiments are carried out according to conventional conditions or conditions recommended by the manufacturer. The reagents or instruments used, unless otherwise specified, are conventional products obtained through commercial channels.

[0033] 1. Embodiment

[0034] Example 1

[0035] Embodiment 1 provides an epoxy resin putty, which is composed of a component A and a component B in a mass ratio of 1:1; in terms of mass percentage, the component A is composed of the following raw materials: 20% of a bio-based epoxy resin monomer, 60% of a bisphenol A epoxy resin (model E-51, epoxy value of 0.48-0.54 mol / L, volatile matter content ≤1.8%), and the balance of ethylene glycol glycidyl ether; in terms of mass percentage, the component B is composed of the following raw materials: 90% of an alicyclic amine-modified epoxy curing agent (model H-3316), 2% of 2,4,6-tris(dimethylaminomethyl)phenol, 7% of 600 mesh silicon powder, and the balance of tin-containing Schiff base-modified carbon nanotubes.

[0036] The preparation process of bio-based epoxy resin monomer is as follows:

[0037]

[0038] (1) According to the molar ratio of chelidonic acid, allyl bromide and triethylamine of 1:3.6:2.2, chelidonic acid, allyl bromide and triethylamine were added to a mixed solution of dimethyl sulfoxide and acetone in a volume ratio of 1:1, and heated and stirred at 195°C for 28 hours. After the reaction, the precipitate was removed by filtration, and the acetone and unreacted allyl bromide and triethylamine were removed by rotary evaporation. Then, dichloromethane was used for extraction, and dimethyl sulfoxide was removed by washing with water. The mixture was dried with anhydrous magnesium sulfate and dichloromethane was removed again by rotary evaporation to obtain intermediate 1;

[0039] (2) The intermediate 1 and meta-chloroperbenzoic acid of step (1) are added to dichloromethane at a molar ratio of 1:2.7, and the reaction is carried out at 40° C. for 3 days. After the reaction is completed, the reaction solution is filtered, washed with 10% sodium sulfate solution, 10% sodium carbonate solution and distilled water in sequence, and then dried with anhydrous magnesium sulfate, and then concentrated by rotary evaporation, washed with ether, and recrystallized to obtain a bio-based epoxy resin monomer.

[0040] The 1H NMR of the above bio-based epoxy resin monomer is as follows Figure 1 As shown: 1 H-NMR (400MHz, DMSO)δ=6.99-6.96(m, 2H), 4.40-4.39(m, 2H), 4.15-4.13(m, 2H), 3.15-3.13(m, 2H), 2.62-2.61(m, 2H), 2.37-2.35(s, 2H). The above results confirmed that the obtained product was the target product.

[0041] The preparation process of tin-containing Schiff base modified carbon nanotubes is as follows:

[0042]

[0043] (a) According to the mass ratio of aminated carbon nanotubes to 2-hydroxy-1-naphthaldehyde of 1:3, the aminated carbon nanotubes were ultrasonically dispersed in chloroform, and then 2-hydroxy-1-naphthaldehyde was added, and the reaction was carried out at 60°C for 3 hours. After the reaction, the carbon nanotubes were dried in air for 3 days and then vacuum dried for 4 hours to obtain Schiff base modified carbon nanotubes;

[0044] (b) The Schiff base-modified carbon nanotubes and triphenyltin chloride prepared in step (a) were added to chloroform in a mass ratio of 1:0.4 and ultrasonically treated for 1 h. The mixture was first dried in air for 3 d and then dried in vacuum for 4 h to obtain tin-containing Schiff base-modified carbon nanotubes.

[0045] Example 1 also provides a method for preparing the above epoxy resin cement, which is as follows:

[0046] I. Preparation of component A: According to the mass percentage, the bio-based epoxy resin monomer, bisphenol A epoxy resin and ethylene glycol glycidyl ether are mixed, stirred evenly, dispersed at high speed for 30 minutes, and vacuum degassed to obtain component A;

[0047] II. Preparation of component B: According to the mass percentage, the alicyclic amine modified epoxy curing agent, 2,4,6-tris (dimethylaminomethyl) phenol, silicon powder and tin-containing Schiff base modified carbon nanotubes are mixed and stirred uniformly, and then dispersed at high speed for 30 minutes and vacuum degassed to obtain component B;

[0048] III. Preparation of epoxy resin putty: According to the mass ratio, component A and component B are mixed evenly, and cured at room temperature for 25 minutes to obtain epoxy resin putty.

[0049] Example 2

[0050] Example 2 provides an epoxy resin putty, which is composed of component A and component B in a mass ratio of 1:0.5; in terms of mass percentage, the component A is composed of the following raw materials: 8% of bio-based epoxy resin monomer, 84% of bisphenol A epoxy resin (model E-51, epoxy value of 0.48-0.54 mol / L, volatile matter content ≤1.8%), and the balance of ethylene glycol glycidyl ether; in terms of mass percentage, the component B is composed of the following raw materials: 88% of alicyclic amine modified epoxy curing agent (model H-3316), 3% of 2,4,6-tris(dimethylaminomethyl)phenol, 8% of 600 mesh silicon powder, and the balance of tin-containing Schiff base modified carbon nanotubes.

[0051] The preparation process of bio-based epoxy resin monomer is as follows:

[0052]

[0053] (1) According to the molar ratio of chelidonic acid, allyl bromide and triethylamine of 1:3.5:2, chelidonic acid, allyl bromide and triethylamine were added to a mixed solution of dimethyl sulfoxide and acetone in a volume ratio of 1:1, and heated and stirred at 190°C for 30 hours. After the reaction, the precipitate was removed by filtration, and the acetone and unreacted allyl bromide and triethylamine were removed by rotary evaporation. Then, dichloromethane was used for extraction, and dimethyl sulfoxide was removed by washing with water. The mixture was dried with anhydrous magnesium sulfate and dichloromethane was removed by rotary evaporation again to obtain intermediate 1;

[0054] (2) The intermediate 1 of step (1) and meta-chloroperbenzoic acid were added to dichloromethane at a molar ratio of 1:2.5, and the reaction was carried out at 35° C. for 3.5 days. After the reaction was completed, the reaction solution was filtered, washed with 10% sodium sulfate solution, 10% sodium carbonate solution and distilled water in sequence, and then dried with anhydrous magnesium sulfate, and then concentrated by rotary evaporation, washed with ether, and recrystallized to obtain a bio-based epoxy resin monomer.

[0055] The preparation process of tin-containing Schiff base modified carbon nanotubes is as follows:

[0056]

[0057] (a) According to the mass ratio of aminated carbon nanotubes to 2-hydroxy-1-naphthaldehyde of 1:1.8, the aminated carbon nanotubes were ultrasonically dispersed in chloroform, and then 2-hydroxy-1-naphthaldehyde was added, and the reaction was carried out at 55°C for 3.5 hours. After the reaction, the carbon nanotubes were dried in air for 3 days and then dried in vacuum for 4 hours to obtain Schiff base modified carbon nanotubes;

[0058] (b) The Schiff base-modified carbon nanotubes and triphenyltin chloride prepared in step (a) were added to chloroform in a mass ratio of 1:0.25 and ultrasonically treated for 0.5 h. The mixture was first dried in air for 3 d and then vacuum dried for 4 h to obtain tin-containing Schiff base-modified carbon nanotubes.

[0059] Example 2 also provides a method for preparing the above epoxy resin cement, which is as follows:

[0060] I. Preparation of component A: According to the mass percentage, the bio-based epoxy resin monomer, bisphenol A epoxy resin and ethylene glycol glycidyl ether are mixed, stirred evenly, dispersed at high speed for 20 minutes, and vacuum degassed to obtain component A;

[0061] II. Preparation of component B: According to the mass percentage, the alicyclic amine modified epoxy curing agent, 2,4,6-tris (dimethylaminomethyl) phenol, silicon powder and tin-containing Schiff base modified carbon nanotubes are mixed and stirred uniformly, and then dispersed at high speed for 20 minutes and vacuum degassed to obtain component B;

[0062] III. Preparation of epoxy resin putty: According to the mass ratio, component A and component B are mixed evenly, and cured at room temperature for 20 minutes to obtain epoxy resin putty.

[0063] Example 3

[0064] Example 3 provides an epoxy resin putty, which is composed of component A and component B in a mass ratio of 1:1.5; in terms of mass percentage, the component A is composed of the following raw materials: 40% of bio-based epoxy resin monomer, 52% of bisphenol A epoxy resin (model E-51, epoxy value of 0.48-0.54 mol / L, volatile matter content ≤1.8%), and the balance of ethylene glycol glycidyl ether; in terms of mass percentage, the component B is composed of the following raw materials: 94.4% of alicyclic amine modified epoxy curing agent (model H-3316), 0.5 of 2,4,6-tris(dimethylaminomethyl)phenol, 5% of 600 mesh silicon powder, and the balance of tin-containing Schiff base modified carbon nanotubes.

[0065] The preparation process of bio-based epoxy resin monomer is as follows:

[0066]

[0067] (1) According to the molar ratio of chelidonic acid, allyl bromide and triethylamine of 1:4:2.5, chelidonic acid, allyl bromide and triethylamine are added to a mixed solution of dimethyl sulfoxide and acetone in a volume ratio of 1:1, and heated and stirred at 200°C for 24 hours. After the reaction is completed, the precipitate is removed by filtration, and the acetone and unreacted allyl bromide and triethylamine are removed by rotary evaporation. Then, dichloromethane is used for extraction, and dimethyl sulfoxide is removed by washing with water. The mixture is dried over anhydrous magnesium sulfate and dichloromethane is removed by rotary evaporation again to obtain intermediate 1;

[0068] (2) The intermediate 1 and meta-chloroperbenzoic acid of step (1) are added to dichloromethane in a molar ratio of 1:3, and the reaction is carried out at 45° C. for 2.5 days. After the reaction is completed, the reaction solution is filtered, washed with 10% sodium sulfate solution, 10% sodium carbonate and distilled water in sequence, and then dried with anhydrous magnesium sulfate, and then concentrated by rotary evaporation, washed with ether, and recrystallized to obtain a bio-based epoxy resin monomer.

[0069] The preparation process of tin-containing Schiff base modified carbon nanotubes is as follows:

[0070]

[0071] (a) According to the mass ratio of aminated carbon nanotubes to 2-hydroxy-1-naphthaldehyde of 1:4.8, the aminated carbon nanotubes were ultrasonically dispersed in chloroform, and then 2-hydroxy-1-naphthaldehyde was added, and the reaction was carried out at 65°C for 2.5 hours. After the reaction, the carbon nanotubes were dried in air for 3 days and then dried in vacuum for 4 hours to obtain Schiff base modified carbon nanotubes;

[0072] (b) The Schiff base-modified carbon nanotubes and triphenyltin chloride prepared in step (a) were added to chloroform in a mass ratio of 1:0.6 and ultrasonically treated for 1.5 h. The mixture was first dried in air for 3 d and then vacuum dried for 4 h to obtain tin-containing Schiff base-modified carbon nanotubes.

[0073] Example 3 also provides a method for preparing the above epoxy resin cement, which is as follows:

[0074] I. Preparation of component A: According to the mass percentage, the bio-based epoxy resin monomer, bisphenol A epoxy resin and ethylene glycol glycidyl ether are mixed, stirred evenly, dispersed at high speed for 40 minutes, and vacuum degassed to obtain component A;

[0075] II. Preparation of component B: According to the mass percentage, the alicyclic amine modified epoxy curing agent, 2,4,6-tris (dimethylaminomethyl) phenol, silicon powder and tin-containing Schiff base modified carbon nanotubes are mixed and stirred uniformly, and then dispersed at high speed for 40 minutes and vacuum degassed to obtain component B;

[0076] III. Preparation of epoxy resin putty: According to the mass ratio, component A and component B are mixed evenly, and cured at room temperature for 30 minutes to obtain epoxy resin putty.

[0077] 2. Comparative Example

[0078] Comparative Example 1

[0079] The difference between Comparative Example 1 and Example 1 is that no bio-based epoxy resin monomer is added to component A, and the rest is the same as Example 1.

[0080] Comparative Example 2

[0081] The difference between Comparative Example 2 and Example 1 is that: the tin-containing Schiff base-modified carbon nanotubes are not added to the B component.

[0082] 3. Test examples

[0083] The mechanical properties and anti-photooxidation properties of the mortar obtained in Examples 1-3 and Comparative Examples 1-2 were tested, and the specific testing process is as follows:

[0084] ① Tensile strength: The test was carried out according to GB / T 2567 standard. Each sample was repeated 5 times. The final experimental result was the average value of the 5 tests. The results are shown in Table 1.

[0085] ② Shear strength: The test was conducted in accordance with the standard GB / T 7124-2008 “Test method for tensile shear strength of adhesives (metal to metal)” and with a CMT6303 universal testing machine (tensile speed 5 mm / min). The results are shown in Table 1.

[0086] ③ Impact strength: GB / T 2571-2021 "Impact test method for resin castings" was used for testing, and an impact testing machine was used for testing. Each sample was repeated 5 times, and the final experimental result was the average of the 5 tests. The results are shown in Table 1;

[0087] ④ Anti-photooxidation performance: Use an ultraviolet radiation lamp with a wavelength of 365nm to irradiate each cement respectively. The mechanical property test results of each cement after irradiation for 10 days are shown in Table 1.

[0088] Table 1

[0089]

[0090] As can be seen from Table 1, the obtained cements of Examples 1-3 have excellent tensile strength, shear strength and impact strength. Before irradiation, the tensile strength, shear strength and impact strength of the cement obtained in Comparative Example 1 were significantly reduced compared with Examples 1-3, which is because the bio-based epoxy resin monomer of the present invention was not added in Comparative Example 1. The bio-based epoxy resin monomer of the present invention is synthesized using chelidonic acid, and the epoxy value of the monomer is relatively high (its epoxy value is calculated to be 0.76). The bio-based epoxy resin monomer is blended and modified with epoxy resin to increase the crosslinking density of the epoxy resin cement, thereby improving its mechanical strength. In addition, flexible groups such as ether bonds and ester groups are introduced into the bio-based epoxy resin monomer, which can improve the flexibility of the epoxy resin cement. Tin-containing Schiff base-modified carbon nanotubes were not added in Comparative Example 2, and the tensile strength, shear strength and impact strength of the obtained cement were slightly reduced.

[0091] In addition, the obtained cements of Examples 1-3 have excellent anti-photooxidation properties. After irradiation, the tensile strength, shear strength and impact strength of the cement obtained in Comparative Example 1 are reduced compared with Examples 1-3, and the tensile strength, shear strength and impact strength of the cement obtained in Comparative Example 2 are significantly reduced. This is because no tin-containing Schiff base-modified carbon nanotubes are added in Comparative Example 2. The present invention is a tin-containing Schiff base-modified carbon nanotube prepared by the joint action of carbon nanotubes, 2-hydroxy-1-naphthaldehyde, and triphenyltin chloride, wherein the carbon nanotubes and the Schiff base enhance their light absorption, and the triphenyltin chloride loaded on the carbon nanotubes acts as an organic tin complex and the Schiff base to remove free radicals, thereby improving the anti-photooxidation property of the epoxy resin cement.

[0092] The above-mentioned embodiments are only preferred embodiments of the present invention and cannot be used to limit the scope of protection of the present invention. Any non-substantial changes and substitutions made by technicians in this field on the basis of the present invention shall fall within the scope of protection required by the present invention.

Claims

1. An epoxy resin putty, characterized in that: The epoxy resin putty comprises component A and component B, wherein the mass ratio of component A to component B is 1:(0.5-1.5); in terms of mass percentage, component A is composed of the following raw materials: 8%-40% of bio-based epoxy resin monomer, 52-84% of epoxy resin, and the balance of diluent; in terms of mass percentage, component B is composed of the following raw materials: 88-94.4% of curing agent, 0.5-3% of accelerator, 5-8% of inorganic filler, and the balance of tin-containing Schiff base modified carbon nanotubes; The preparation process of the bio-based epoxy resin monomer is as follows: (1) adding chelidonic acid, allyl bromide and triethylamine to a mixed solution of dimethyl sulfoxide and acetone for heating and stirring to react, and purifying after the reaction to obtain intermediate 1; (2) adding the intermediate 1 of step (1) and m-chloroperbenzoic acid to dichloromethane for reaction, and purifying after the reaction to obtain a bio-based epoxy resin monomer; The preparation process of the tin-containing Schiff base modified carbon nanotubes is as follows: (a) dispersing the aminated carbon nanotubes in chloroform, then adding 2-hydroxy-1-naphthaldehyde to react, and drying after the reaction to obtain Schiff base modified carbon nanotubes; (b) The Schiff base-modified carbon nanotubes and triphenyltin chloride prepared in step (a) are added to chloroform for ultrasonic treatment, and then dried to obtain tin-containing Schiff base-modified carbon nanotubes.

2. The epoxy resin cement as claimed in claim 1, characterized in that The molar ratio of chelidonic acid, allyl bromide and triethylamine in step (1) is 1:(3.5-4):(2-2.5); the temperature of the heating and stirring reaction is 190-200°C, and the heating and stirring reaction time is 24-30h; the volume ratio of dimethyl sulfoxide and acetone is 1:

1.

3. The epoxy resin cement as claimed in claim 1, characterized in that In step (2), the molar ratio of the intermediate 1 to m-chloroperbenzoic acid is 1:(2.5-3), the reaction temperature is 35-45° C., and the reaction time is 2.5-3.5 days.

4. The epoxy resin cement as claimed in claim 1, characterized in that In step (a), the mass ratio of the amino carbon nanotubes to 2-hydroxy-1-naphthaldehyde is 1:(1.8-4.8), the reaction temperature is 55-65° C., and the reaction time is 2.5-3.5 hours.

5. The epoxy resin cement as claimed in claim 1, characterized in that In step (b), the mass ratio of the Schiff base modified carbon nanotubes to triphenyltin chloride is 1:(0.25-0.6), and the ultrasonic treatment time is 0.5-1.5h.

6. The epoxy resin cement as claimed in claim 1, characterized in that The epoxy resin is bisphenol A epoxy resin; the diluent is ethylene glycol glycidyl ether; the curing agent is alicyclic amine modified epoxy curing agent; the accelerator is 2,4,6-tris(dimethylaminomethyl)phenol; and the inorganic filler is silicon micropowder.

7. The method for preparing epoxy resin cement according to claim 1, characterized in that: The following steps are involved: .Preparing component A: According to the mass percentage, the bio-based epoxy resin monomer, epoxy resin and diluent are mixed, stirred evenly, and subjected to high-speed dispersion and vacuum degassing to obtain component A; .Preparing component B: According to the mass percentage, the curing agent, the accelerator, the inorganic filler and the tin-containing Schiff base modified carbon nanotubes are mixed and stirred uniformly, and the component B is obtained by high-speed dispersion and vacuum degassing; .Prepare epoxy resin putty: Mix component A and component B evenly according to the mass ratio, and obtain epoxy resin putty after curing at room temperature.

8. The method for preparing epoxy resin cement according to claim 7, characterized in that: Step I The high-speed dispersion time is 20-40 minutes, and the curing time is 20-30 minutes.

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