Preparation method of waterproof and oil-proof flexible epoxy resin

Abstract

The invention relates to the technical field of epoxy resin materials, and discloses a waterproof and oil-proof flexible epoxy resin preparation method, which comprises: 1, completely mixing and stirring an epoxy resin, an anti-aging basalt fiber, a leveling agent, an ultraviolet light absorber, a defoaming agent and acetone to obtain a mixture; and 2, uniformly mixing a waterproof and oil-proof curing agent with the mixture, and heating and curing to obtain the waterproof and oil-proof flexible epoxy resin. The epoxy resin material prepared by the invention has excellent flexibility and wear resistance, is not easy to damage when being impacted and rubbed, also has excellent waterproof and oil-proof performance, strong hydrophobicity and excellent antifouling effect, has self-cleaning capability when being used for a long time, and can meet the use requirements in various environments.

Description

Technical Field

[0001] The present invention relates to the technical field of epoxy resin materials, and particularly relates to a preparation method of a waterproof and oil-proof flexible epoxy resin. Background Art

[0002] Epoxy resin is a general term for a class of polymers containing two or more epoxy groups in its molecular structure. The epoxy groups in its structure can undergo ring-opening addition reactions under appropriate catalysts and temperatures to form a three-dimensional network structure of high-molecular compounds. Epoxy resin materials have excellent electrical insulation and adhesiveness, and are widely used in the fields of potting insulation of electronic components and circuits, plastic encapsulation of semiconductor components, structural adhesives, daily necessities, construction adhesives, etc. However, in actual use, epoxy resin has poor anti-aging ability, is not resistant to high temperatures, its impact resistance and wear resistance need to be improved, and it does not have the ability to be waterproof and oil-proof, making it difficult to meet the usage requirements in various environments.

[0003] The patent with the publication number CN108912609B discloses an epoxy resin composite material and its preparation method, including the following steps: mixing epoxy resin, toughening modifier, surfactant, foaming agent and flame retardant to obtain a premix; adding the premix from the main feeding port of a single-screw extruder, adding filler fibers and curing agent from the side feeding port, and extruding from the screw die head to obtain a blend; heating and curing the blend through a high-temperature drying channel to obtain an epoxy resin composite material with high strength, high toughness, flame retardant and lightweight characteristics; however, this kind of epoxy resin does not have the ability to be waterproof and oil-proof, and does not have a self-cleaning effect, greatly limiting its use in water and oil-polluted environments. Summary of the Invention

[0004] The purpose of the present invention is to provide a waterproof and oil-proof flexible epoxy resin, which solves the following technical problems: (1) the problem that ordinary epoxy resin has poor waterproof and oil-proof performance and does not have a self-cleaning effect; (2) the problem that ordinary epoxy resin has poor flexibility and wear resistance and is easily damaged when subjected to impact and friction; (3) the problem that ordinary epoxy resin has poor heat resistance and anti-aging ability, its durability needs to be improved, and its service life is short.

[0005] The purpose of the present invention can be achieved through the following technical solutions: A preparation method of a waterproof and oil-proof flexible epoxy resin, including the following steps: Step 1: Fully mix and stir epoxy resin, anti-aging basalt fiber, leveling agent, ultraviolet absorber, defoaming agent, and acetone to obtain a mixture; Step 2: Mix the waterproof and oil-proof curing agent with the mixture evenly, heat up to 120 - 125 °C and cure for 15 - 25 min to obtain the waterproof and oil-proof flexible epoxy resin.

[0006] Furthermore, the waterproof and oil-proof flexible epoxy resin comprises the following raw materials in parts by weight: 60-80 parts of epoxy resin, 6-8 parts of anti-aging basalt fiber, 1-3 parts of leveling agent, 2-3 parts of ultraviolet absorber, 1-2 parts of defoaming agent, 20-25 parts of waterproof and oil-proof curing agent, and 100-150 parts of acetone.

[0007] Furthermore, the epoxy resin is any one of bisphenol A epoxy resin and bisphenol F epoxy resin; the leveling agent is any one of polyurethane leveling agent and butyl acrylate; the ultraviolet absorber is any one of ultraviolet absorber UV-P, ultraviolet absorber UV-531, and ultraviolet absorber UV-1130; the defoaming agent is any one of dimethyl silicone oil defoaming agent and fatty alcohol polyoxyethylene ether defoaming agent.

[0008] Furthermore, the preparation of the anti-aging basalt fiber comprises the following steps: S1: Place the basalt fiber in N,N-dimethylformamide, ultrasonically disperse for 10-12 min, then transfer it to a reaction kettle, add epichlorohydrin and tetrabutylammonium bromide, start heating up, and keep it at 90-95 °C for 2-3 h when the temperature reaches, cool down to 60-65 °C, add sodium hydroxide solution, stir for 1-1.5 h and then stop heating, filter, wash, and dry to obtain epoxidized basalt fiber; S2: Place the epoxidized basalt fiber in toluene, ultrasonically disperse for 15-18 min, add rhein and tetrabutylammonium bromide, heat up and react, filter, wash, and dry to obtain anti-aging basalt fiber.

[0009] In this solution, under the action of tetrabutylammonium bromide and sodium hydroxide, epichlorohydrin modifies the surface of basalt fiber, undergoes ring-opening and then ring-closing reaction to obtain epoxidized basalt fiber. Then, under the action of tetrabutylammonium bromide, the epoxy groups on the surface of epoxidized basalt fiber undergo ring-opening reaction with the carboxyl groups in the rhein structure to obtain anti-aging basalt fiber. This kind of anti-aging basalt fiber has multiple active hydroxyl groups on its surface, can be evenly dispersed in the epoxy resin matrix material and participate in the epoxy resin curing reaction, can effectively enhance the wear resistance and flexibility of the epoxy resin material. At the same time, the rhein grafted on its surface, as a polyphenolic substance, can scavenge free radicals and inhibit the activity of oxidase, thus inhibiting the occurrence of oxidation reaction, achieving excellent antioxidant effect, and effectively improving the anti-aging ability of the epoxy resin material.

[0010] Furthermore, in step S1, the diameter of the basalt fiber is 12 μm and the length is 1 mm.

[0011] Furthermore, in step S1, the mass fraction of the sodium hydroxide solution is 12-15%.

[0012] Further, in step S2, the temperature for the temperature-raising reaction is 85-90 °C, and the time is 5-6 h.

[0013] Further, the preparation method of the waterproof and oil-proof curing agent includes the following steps: SS1: Place the hydroxyl-terminated alkyd resin and 2-(trifluoromethyl)acrylic acid in 65 ml of xylene, mix and stir well, add a catalyst, raise the temperature to 90-95 °C and react for 3-5 h, and remove the solvent by vacuum distillation to obtain a modified alkyd resin; SS2: Place the modified alkyd resin and cis-5-norbornene-exo-2,3-dicarboxylic anhydride in absolute ethanol, add an initiator, raise the temperature to 45-50 °C and react for 5-8 h, and remove the solvent by vacuum distillation to collect the product to obtain a waterproof and oil-proof curing agent.

[0014] In this solution, under the action of a catalyst, the hydroxyl group in the structure of the hydroxyl-terminated alkyd resin reacts with the carboxyl group in the structure of 2-(trifluoromethyl)acrylic acid to obtain a modified alkyd resin containing organofluorine in the structure. Then, under the action of an initiator, the alkenyl group in the structure of the modified alkyd resin reacts with the alkenyl group in the structure of cis-5-norbornene-exo-2,3-dicarboxylic anhydride to undergo a free radical polymerization reaction to obtain a waterproof and oil-proof curing agent. Both ends of the structure of this waterproof and oil-proof curing agent have an anhydride structure and can be used as an epoxy resin curing agent. By crosslinking the long-chain alkyd resin with the epoxy resin chain segments, a three-dimensional network structure is formed, effectively enhancing the compactness of the epoxy resin material structure and improving the flexibility of the epoxy resin material. The norbornene structure in its structure can effectively enhance the heat resistance and wear resistance of the epoxy resin. At the same time, it contains a large amount of organofluorine in its structure, has an extremely low surface energy, the carbon-fluorine bond formed has a high bond energy and a short bond length, has excellent chemical stability, and can effectively enhance the waterproof and oil-proof ability of the epoxy resin, making it have an excellent anti-fouling effect.

[0015] Further, in step SS1, the catalyst is p-toluenesulfonic acid.

[0016] Further, in step SS2, the initiator is any one of benzoyl peroxide and diisopropylbenzene peroxide.

[0017] The beneficial effects of the present invention: By preparing anti-aging basalt fibers and a waterproof and oil-proof curing agent and participating in the preparation process of epoxy resin, the prepared epoxy resin material has excellent flexibility and wear resistance, is not easily damaged when impacted and rubbed, and at the same time has excellent waterproof and oil-proof properties, strong hydrophobicity, excellent anti-fouling effect, and the ability of self-cleaning during long-term use, and can meet the use requirements in various environments.

[0018] Of course, it is not necessary for any product implementing the present invention to simultaneously achieve all the above-mentioned advantages. BRIEF DESCRIPTION OF THE DRAWINGS

[0019] In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the accompanying drawings required for describing the embodiments will be briefly introduced below. Obviously, the accompanying drawings in the following description are only some embodiments of the present invention, and for those of ordinary skill in the art, other drawings can be obtained based on these drawings without creative efforts.

[0020] Figure 1 It is a flowchart for the preparation of the waterproof and oil-proof flexible epoxy resin of the present invention. DETAILED DESCRIPTION OF THE EMBODIMENTS

[0021] The technical solutions in the embodiments of the present invention will be clearly and completely described below in conjunction with the accompanying drawings in the embodiments of the present invention. Obviously, the described embodiments are only a part of the embodiments of the present invention, rather than all the embodiments. All other embodiments obtained by those of ordinary skill in the art based on the embodiments of the present invention without creative efforts fall within the scope of protection of the present invention.

[0022] The preparation methods of the anti-aging basalt fiber and the waterproof and oil-proof curing agent in the following embodiments and comparative examples of the present invention are as follows: I. Preparation of Anti-aging Basalt Fiber S1: Place 2 g of basalt fibers with a diameter of 12 μm and a length of 1 mm in 80 ml of N,N-dimethylformamide. After ultrasonic dispersion for 10 min, transfer it to a reaction kettle, add 1.8 g of epichlorohydrin and 0.3 g of tetrabutylammonium bromide, start heating up. When the temperature reaches 90 °C, maintain for 2 h, cool down to 60 °C, add 2 ml of sodium hydroxide solution with a mass fraction of 12%, stir for 1 h and then stop heating. After filtration, washing and drying, epoxidized basalt fibers are obtained; The content of epoxy groups in epoxy - modified basalt fibers was determined by the pyridine hydrochloride method. Weighed 2 g of epoxy - modified basalt fibers as a sample, added 30 ml of hydrochloric acid - pyridine solution, heated under reflux for 0.5 h, cooled to room temperature, added 15 ml of neutral acetone for rinsing, then dropped 1 ml of phenolphthalein indicator, and titrated with a 1 - mol / L sodium hydroxide ethanol standard solution until the solution changed color to stop the reaction. At the same time, a blank test was carried out. Calculate the content of epoxy groups in the sample according to the following formula: Content of epoxy groups (%)=(V - V0)C / 1000M; where V is the volume of the sodium hydroxide ethanol standard solution consumed when titrating the sample solution, in ml; V0 is the volume of the sodium hydroxide ethanol standard solution consumed in the blank experiment, in ml; C is the concentration of the sodium hydroxide ethanol standard solution, in mol / L; M is the mass of the sample, in g. After calculation, the content of epoxy groups in epoxy - modified basalt fibers is 7.9%. S2: Placed 2.6 g of epoxy - modified basalt fibers in 100 ml of toluene, ultrasonically dispersed for 15 min, then added 2.5 g of rhein and 0.5 g of tetrabutylammonium bromide, heated to 85 °C and reacted for 5 h. After filtration, washing and drying, anti - aging basalt fibers were obtained.

[0023] The pyridine hydrochloride method was used to test the content of epoxy groups in the anti - aging basalt fibers. The specific operation steps were the same as those in step S1. After calculation, the content of epoxy groups in the anti - aging basalt fibers was 0.3%. Compared with the content of epoxy groups in the epoxy - modified basalt fibers, the content of epoxy groups in the anti - aging basalt fibers decreased significantly because the epoxy groups on the surface of the epoxy - modified basalt fibers were consumed after undergoing a ring - opening reaction with the carboxyl groups in the structure of rhein.

[0024] II. Preparation of waterproof and oil - proof curing agent SS1: Put 3 g of hydroxyl - terminated alkyd resin and 2.8 g of 2 - (trifluoromethyl) acrylic acid into 65 ml of xylene, stirred well, added 0.3 g of p - toluenesulfonic acid, heated to 90 °C and reacted for 3 h. After removing the solvent by vacuum distillation, a modified alkyd resin was obtained. 2g of modified alkyd resin was used as a sample, and the double bond content in its structure was tested by iodine titration. 30ml of carbon tetrachloride was placed in an iodine volumetric flask, and the sample and 15ml of potassium bromide were added. After shaking, 6ml of 10% potassium iodide solution and 8ml of distilled water were added and shaken. A 0.1mol / L sodium thiosulfate standard solution was used for titration. When the color changed, 1ml of 1% starch solution was added, and the titration was continued to the reaction end point. A blank control was also performed. The double bond content in the sample was calculated according to the following formula: Double bond content in sample (%) = (V0−V1)C×0.05×74 / M; where V0 is the volume of sodium thiosulfate consumed in the blank test, ml; V1 is the volume of sodium thiosulfate consumed in the titration sample, ml; C is the concentration of the sodium thiosulfate solution, mol / L; After calculation, the double bond content in the modified alkyd resin is 8.8%.

[0025] SS2: 3.5 g of modified alkyd resin and 3 g of cis-5-norbornene-exo-2,3-dicarboxylic anhydride were placed in 80 ml of anhydrous ethanol, 0.6 g of benzoyl peroxide was added, the temperature was raised to 45°C and reacted for 5 h, the solvent was removed by vacuum distillation, and the product was collected to obtain a waterproof and oil-proof curing agent.

[0026] The double bond content in the waterproof and oil-proof curing agent was detected by iodine titration. The specific operation method was the same as step SS1. After calculation, the double bond content in the waterproof and oil-proof curing agent was 1.6%, which was significantly reduced compared with the double bond content in the modified alkyd resin. This was due to the free radical polymerization reaction between the double bonds in the modified alkyd resin structure and the double bonds in the cis-5-norbornene-exo-2,3-dicarboxylic anhydride structure, resulting in consumption.

[0027] Example 1 Preparation of Waterproof and Oilproof Flexible Epoxy Resin Step 1: 60 parts of bisphenol A epoxy resin, 6 parts of anti-aging basalt fiber, 1 part of polyurethane leveling agent, 2 parts of UV absorber UV-P, 1 part of dimethyl silicone oil defoamer and 100 parts of acetone are mixed and stirred to obtain a mixture; Step 2: Evenly mix 20 parts of waterproof and oil-proof curing agent with the mixture, heat to 120° C. and cure for 15 minutes to obtain a waterproof and oil-proof flexible epoxy resin.

[0028] Example 2

[0029] Preparation of Waterproof and Oilproof Flexible Epoxy Resin Step 1, 70 parts of bisphenol A epoxy resin, 7 parts of anti-aging basalt fiber, 2 parts of butyl acrylate, 2.5 parts of ultraviolet absorber UV-531, 1.5 parts of fatty alcohol polyoxyethylene ether and 120 parts of acetone are mixed and stirred to obtain a mixture; Step 2: Mix 23 parts of the waterproof and oil-proof curing agent evenly with the mixture, heat it up to 123°C and cure for 20 minutes to obtain the waterproof and oil-proof flexible epoxy resin.

[0030] Example 3

[0031] Preparation of Waterproof and Oil-proof Flexible Epoxy Resin Step 1: Thoroughly mix and stir 80 parts of bisphenol F type epoxy resin, 6 parts of anti-aging basalt fiber, 3 parts of polyurethane leveling agent, 3 parts of ultraviolet absorber UV-1130, 2 parts of dimethyl silicone oil defoamer with 150 parts of acetone to obtain a mixture; Step 2: Mix 25 parts of the waterproof and oil-proof curing agent evenly with the mixture, heat it up to 125°C and cure for 25 minutes to obtain the waterproof and oil-proof flexible epoxy resin.

[0032] Comparative Example 1 Preparation of Epoxy Resin Step 1: Thoroughly mix and stir 70 parts of bisphenol A type epoxy resin, 2 parts of butyl acrylate, 2.5 parts of ultraviolet absorber UV-531, 1.5 parts of fatty alcohol polyoxyethylene ether with 120 parts of acetone to obtain a mixture; Step 2: Mix 23 parts of the waterproof and oil-proof curing agent evenly with the mixture, heat it up to 123°C and cure for 20 minutes to obtain the waterproof and oil-proof flexible epoxy resin.

[0033] Comparative Example 2 Preparation of Epoxy Resin Step 1: Thoroughly mix and stir 70 parts of bisphenol A type epoxy resin, 7 parts of anti-aging basalt fiber, 2 parts of butyl acrylate, 2.5 parts of ultraviolet absorber UV-531, 1.5 parts of fatty alcohol polyoxyethylene ether with 120 parts of acetone to obtain a mixture; Step 2: Mix 23 parts of phthalic anhydride evenly with the mixture, heat it up to 123°C and cure for 20 minutes to obtain the waterproof and oil-proof flexible epoxy resin.

[0034] Comparative Example 3 Preparation of Epoxy Resin Step 1: Thoroughly mix and stir 70 parts of bisphenol A type epoxy resin, 7 parts of epoxy basalt fiber, 2 parts of butyl acrylate, 2.5 parts of ultraviolet absorber UV-531, 1.5 parts of fatty alcohol polyoxyethylene ether with 120 parts of acetone to obtain a mixture; Step 2: Mix 23 parts of the waterproof and oil-proof curing agent evenly with the mixture, heat it up to 123°C and cure for 20 minutes to obtain the waterproof and oil-proof flexible epoxy resin.

[0035] Performance Testing The epoxy resins prepared in Examples 1 - 3 and Comparative Examples 1 - 3 were made into samples that met the specifications.

[0036] ① Refer to the standard GB / T1040 - 2006 to conduct tensile strength tests on the samples and the samples after being treated in an aging oven at 80°C for 72 h; refer to the standard GB / T1043 - 2008 to test the impact strength of the samples to judge the impact resistance ability of the samples; refer to the standard GB / T1633 - 2000 to test the Vicat softening temperature of the samples to judge the high - temperature resistance performance of the samples; use an SDC - 100S type contact angle tester to test the water contact angle and oil contact angle of the samples; use a Taber type abrasion tester to test the abrasion resistance of the samples. Place two grinding wheels on the samples, set the moving speed of the grinding wheels at 50 r / min to conduct wear experiments on the samples, record the initial mass of the samples, and the mass of the samples after 20,000 revolutions of wear. Use the following formula to calculate the abrasion value of the samples: m = m1 - m2; where m is the abrasion value of the samples, g / 20,000 r; m1 is the initial mass of the samples, g; m2 is the mass of the samples after wear, g; the smaller the abrasion value, the better the abrasion resistance performance of the samples; the specific test results are shown in Table 1 below; Table 1:

[0037] As can be seen from Table 1 above, the samples prepared in Examples 1 - 3 all have excellent mechanical strength, anti - aging ability, impact resistance performance, and high - temperature resistance performance. In the sample prepared in Comparative Example 1, anti - aging basalt fibers were not added, so the anti - aging ability is poor. In the sample prepared in Comparative Example 2, a waterproof and oil - proof curing agent was not added, and the high - temperature resistance performance is inferior to that of the examples. In the sample prepared in Comparative Example 3, epoxy - coated basalt fibers were directly added, and rhein was not coated on the surface of the basalt fibers, so the anti - aging ability is poor.

[0038] ② Use an SDC - 100S type contact angle tester to test the water contact angle and oil contact angle of the samples; use a Taber type abrasion tester to test the abrasion resistance of the samples. Place two grinding wheels on the samples, set the moving speed of the grinding wheels at 50 r / min to conduct wear experiments on the samples, record the initial mass of the samples, and the mass of the samples after 20,000 revolutions of wear. Use the following formula to calculate the abrasion value of the samples: m = m1 - m2; where m is the abrasion value of the samples, g / 20,000 r; m1 is the initial mass of the samples, g; m2 is the mass of the samples after wear, g; the smaller the abrasion value, the better the abrasion resistance performance of the samples; the specific test results are shown in Table 2 below; Table 2:

[0039] As can be seen from Table 2 above, the samples prepared in Examples 1-3 have good water and oil repellency and wear resistance. In the sample prepared in Comparative Example 1, anti-aging basalt fibers were not added, so the wear resistance is poor. In the sample prepared in Comparative Example 2, a water and oil repellent curing agent was not added, so the water and oil repellent effects are poor. In the sample prepared in Comparative Example 3, epoxy basalt fibers were directly added, and a water and oil repellent curing agent was also added, so both the water and oil repellent performance and the wear resistance are good.

[0040] In the description of this specification, the description with reference to terms such as "one embodiment", "some embodiments", "example", "specific example", or "some examples" means that the specific features, structures, materials, or characteristics described in connection with the embodiment or example are included in at least one embodiment or example of the present invention. In this specification, the schematic representations 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 a suitable manner in any one or more embodiments or examples. In addition, without contradiction, those skilled in the art can combine and combine the different embodiments or examples described in this specification and the features of different embodiments or examples.

[0041] The above content is only an example and illustration of the concept of the present invention. Those skilled in the art of this technology can make various modifications or supplements to the specific embodiments described or use similar methods to replace them, as long as they do not deviate from the scope defined by the concept of the invention, they should all fall within the protection scope of the present invention.

Claims

1. A method for preparing a waterproof and oil-proof flexible epoxy resin, characterized in that: The following steps are involved: Step 1: Fully mix and stir epoxy resin, anti-aging basalt fiber, leveling agent, ultraviolet absorber, defoamer and acetone to obtain a mixture; Step 2: Evenly mix the waterproof and oil-proof curing agent with the mixed material, heat to 120-125° C. and cure for 15-25 minutes to obtain a waterproof and oil-proof flexible epoxy resin.

2. The method for preparing a waterproof and oil-proof flexible epoxy resin according to claim 1, characterized in that: The waterproof and oil-proof flexible epoxy resin comprises the following raw materials in parts by weight: 60-80 parts of epoxy resin, 6-8 parts of anti-aging basalt fiber, 1-3 parts of leveling agent, 2-3 parts of ultraviolet absorber, 1-2 parts of defoamer, 20-25 parts of waterproof and oil-proof curing agent, and 100-150 parts of acetone.

3. The method for preparing a waterproof and oil-proof flexible epoxy resin according to claim 1, characterized in that: The epoxy resin is any one of bisphenol A epoxy resin and bisphenol F epoxy resin; the leveling agent is any one of polyurethane leveling agent and butyl acrylate; the ultraviolet absorber is any one of ultraviolet absorber UV-P, ultraviolet absorber UV-531, and ultraviolet absorber UV-1130; the defoamer is any one of dimethyl silicone oil defoamer and fatty alcohol polyoxyethylene ether defoamer.

4. The method for preparing a waterproof and oil-proof flexible epoxy resin according to claim 1, characterized in that: The method for preparing the anti-aging basalt fiber comprises the following steps: S1: Place basalt fiber in N,N-dimethylformamide, ultrasonically disperse for 10-12 minutes, transfer to a reactor, add epichlorohydrin and tetrabutylammonium bromide, start heating, and when the temperature reaches 90-95°C, maintain for 2-3 hours, cool to 60-65°C, add sodium hydroxide solution, stir for 1-1.5 hours, then stop heating, filter, wash, and dry to obtain epoxidized basalt fiber; S2: The epoxidized basalt fiber is placed in toluene, and after ultrasonic dispersion for 15-18 minutes, rhein and tetrabutylammonium bromide are added, and the temperature is raised to react. After filtering, washing and drying, the anti-aging basalt fiber is obtained.

5. The method for preparing a waterproof and oil-proof flexible epoxy resin according to claim 4, characterized in that: In step S1, the diameter of the basalt fiber is 12 μm and the length is 1 mm.

6. The method for preparing a waterproof and oil-proof flexible epoxy resin according to claim 4, characterized in that: In step S1, the mass fraction of the sodium hydroxide solution is 12-15%.

7. The method for preparing a waterproof and oil-proof flexible epoxy resin according to claim 4, characterized in that: In step S2, the temperature of the temperature-raising reaction is 85-90° C. and the time is 5-6 hours.

8. The method for preparing a waterproof and oil-proof flexible epoxy resin according to claim 1, characterized in that: The preparation method of the waterproof and oil-proof curing agent comprises the following steps: SS1: Place the terminal hydroxyl alkyd resin and 2-(trifluoromethyl) acrylic acid in xylene, mix and stir thoroughly, add a catalyst, heat to 90-95°C for reaction for 3-5h, remove the solvent after reduced pressure distillation, and obtain a modified alkyd resin; SS2: Place the modified alkyd resin and cis-5-norbornene-exo-2,3-dicarboxylic anhydride in anhydrous ethanol, add an initiator, heat to 45-50°C and react for 5-8h, remove the solvent after reduced pressure distillation, and collect the product to obtain a waterproof and oil-proof curing agent.

9. The method for preparing a waterproof and oil-proof flexible epoxy resin according to claim 8, characterized in that: In step SS1, the catalyst is p-toluenesulfonic acid.

10. The method for preparing a waterproof and oil-proof flexible epoxy resin according to claim 8, characterized in that: In step SS2, the initiator is any one of benzoyl peroxide and diisopropylbenzene peroxide.

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