Underwater fast-curing modified epoxy resin plugging material and preparation method thereof

Abstract

The invention relates to the technical field of leaking stoppage materials, and particularly discloses an underwater fast-curing modified epoxy resin leaking stoppage material and a preparation method thereof. A polyether chain segment, a phenolic skeleton and a lignin skeleton are introduced through the lignin-based phenolic amine curing agent, and curing of epoxy resin is promoted through phenolic hydroxyl groups. In the traditional plugging technology, the modified epoxy resin for reinforcement is difficult to cure under the conditions of low temperature and flowing water, but the underwater fast-curing modified epoxy resin plugging material can overcome the adverse effect of the underwater environment on the curing effect, and a cured body with relatively good strength and flexibility can be obtained, so that the defects in the related technology are overcome, and the underwater fast-curing modified epoxy resin plugging material has good application prospects. And the leaking stoppage requirement is fully met.

Description

Technical Field

[0001] The present application relates to the technical field of plugging materials, and more specifically, to an underwater fast-setting modified epoxy resin plugging material and a preparation method thereof. Background Art

[0002] With the rapid development of the national economy, the infrastructure construction in China has witnessed an explosive growth. The designed service life of subway projects is up to a hundred years. However, in subway and underground projects, there are often complex geological conditions, connections between new and old structures, and combinations between different types of structures. Due to factors such as the shrinkage of concrete itself, construction errors, and groundwater, cracks and defects in subway concrete structures inevitably have a certain degree of water leakage. The existence of water leakage not only brings potential safety hazards to the safe operation of the subway, but also greatly affects the durability of the concrete structure, seriously affecting the service life of the subway system.

[0003] Epoxy resin grouting materials have strong adhesion, low shrinkage rate, and good chemical corrosion resistance. They have good bonding properties with concrete, metal, etc., and can play both the roles of plugging and reinforcement. They are one of the most widely used reinforcing materials in domestic grouting materials and are commonly used in projects such as concrete crack repair, complex foundation treatment, anti-seepage plugging, and reinforcement. The curing rate of epoxy resin is greatly affected by temperature. Research shows that for every 10°C decrease in temperature, the curing time may be extended by 2 - 4 times, or even lead to incomplete curing. In an underwater environment, on the one hand, the low temperature will cause the reaction to be sluggish, and on the other hand, due to the high specific heat capacity of water, it will absorb the heat of the curing system, resulting in the stagnation of the curing reaction. Coupled with the dilution and stripping effects of flowing water and the influence of water on the wettability of the interface, it is difficult for epoxy resin grouting materials to achieve the desired effect.

[0004] Regarding the above related technologies, the inventor believes that although epoxy resin grouting materials can be applied to anti-seepage plugging operations, when there is already accumulated water in the construction area to be treated, the curing rate of epoxy resin grouting materials will be greatly affected, and it will further magnify the defect of poor flexibility of epoxy resin, making it difficult to fully meet the plugging requirements. Summary of the Invention

[0005] In the related technologies, when there is already accumulated water in the construction area to be treated, the curing rate of epoxy resin grouting materials will be greatly affected, and it will further magnify the defect of poor flexibility of epoxy resin, making it difficult to fully meet the plugging requirements. To improve this defect, the present application provides an underwater fast-setting modified epoxy resin plugging material and a preparation method thereof.

[0006] In the first aspect, the present application provides an underwater fast-setting modified epoxy resin plugging material, adopting the following technical solution: An underwater fast-curing modified epoxy resin plugging material, comprising component A and component B. Component A includes epoxy resin, filler and diluent. Component B includes lignin-based phenolic amine curing agent, silane coupling agent and curing accelerator. The filler is selected as lignin fiber. The lignin-based phenolic amine curing agent is prepared by Mannich reaction of active hydrogen donor, aldehyde compound and amine compound. The active hydrogen donor includes lignin-based polyphenol compound, and the amine compound includes polyether amine and triethylenetetramine.

[0007] By adopting the above technical solution, the present application selects a lignin-based phenolic amine curing agent to cure epoxy resin. The lignin-based phenolic amine curing agent of the present application is prepared by Mannich reaction of active hydrogen donor, aldehyde compound and amine compound, and has a phenolic aldehyde skeleton and a lignin skeleton in the molecule, and has relatively high strength performance. The present application also defines that the filler is lignin fiber, and the lignin fiber has good compatibility with the lignin-based phenolic amine curing agent, and can cooperate with the phenolic aldehyde skeleton and the lignin skeleton to improve the strength performance of the epoxy resin cured body. In the lignin-based phenolic amine curing agent, the lignin-based polyphenol compound is used as an active hydrogen donor, introducing phenolic hydroxyl groups into the system. The phenolic hydroxyl groups can promote the curing of epoxy resin, so it can show a relatively high curing rate underwater. The addition of polyether amine enables the lignin-based phenolic amine curing agent to contain polyether segments, and the polyether segments can effectively improve the flexibility of epoxy resin, overcoming the defect of poor flexibility of epoxy resin. Through the synergistic effect of the above components, the underwater fast-curing modified epoxy resin plugging material of the present application can be quickly cured even in a construction area with accumulated water, and can overcome the adverse effects of the underwater environment on the curing effect, and can obtain a cured body with good strength and flexibility, thus overcoming the defects in the related technology and fully meeting the plugging requirements.

[0008] Preferably, component A is mixed with the following raw materials in parts by weight: 115-125 parts of epoxy resin, 5-7 parts of filler, and 20-30 parts of diluent.

[0009] By adopting the above technical solution, the present application optimizes the raw material composition of component A. With the assistance of the filler and diluent, the epoxy resin can maintain good strength and flexibility after curing.

[0010] Preferably, component B is mixed with the following raw materials in parts by weight: 60-70 parts of lignin-based phenolic amine curing agent, 1-1.5 parts of silane coupling agent, and 2-3 parts of curing accelerator.

[0011] By adopting the above technical solution, the present application optimizes the raw material composition of component B. With the assistance of the silane coupling agent and curing accelerator, the epoxy resin can maintain good strength and flexibility after curing.

[0012] Preferably, the lignin-based phenolic amine curing agent is prepared according to the following method: Mix the active hydrogen donor and the amine compound, stir and preheat the mixture, add the aldehyde compound, then carry out heating under reflux reaction, cool after the reaction ends, and carry out vacuum dehydration on the product to obtain the lignin-based phenolic amine curing agent.

[0013] By adopting the above technical solution, the present application prepares the lignin-based phenolic amine curing agent through the Mannich reaction. During the reaction process, the lignin-based polyphenol compound participates in the reaction through the hydrogen atoms at the ortho and para positions of the phenolic hydroxyl group and the α position of the side chain carbonyl group, and combines with the amine compound under the action of the aldehyde compound to obtain the lignin-based phenolic amine curing agent.

[0014] Preferably, the lignin-based polyphenol compound is prepared according to the following method: Mix the molten phenol and water, then add the catalyst and the lignin raw material to obtain a reaction mixture, stir the reaction mixture under constant temperature conditions, cool with cold water after the reaction ends to obtain a crude product, add dioxane to the crude product, then centrifuge to remove impurities, add anhydrous ether to the residue for precipitation, and obtain the lignin-based polyphenol compound after freeze-drying.

[0015] By adopting the above technical solution, the present application carries out phenolic treatment on the lignin raw material with phenol. The phenolic treatment can further increase the content of phenolic hydroxyl groups on the basis of the lignin raw material, thereby improving the promoting effect of phenolic hydroxyl groups on the curing of epoxy resin and helping to improve the curing rate of the epoxy resin plugging material.

[0016] Preferably, the catalyst is selected from one of aluminum chloride, calcium chloride, and ammonium acetate.

[0017] By adopting the above technical solution, the present application optimizes the type of catalyst. Among the above catalysts, aluminum chloride, as a strong Lewis acid, can more efficiently promote the phenolic treatment of the lignin raw material, help to improve the curing rate of the epoxy resin plugging material, and the corrosion of aluminum chloride itself is small, thus playing a certain protective role for the equipment.

[0018] Preferably, the catalyst is selected from aluminum chloride, and the dosage of the catalyst is 4.5-5.5% of the total weight of the lignin raw material.

[0019] By adopting the above technical solution, the present application optimizes the dosage of aluminum chloride, which helps to improve the curing rate of the epoxy resin plugging material.

[0020] Preferably, the lignin raw material is selected from at least one of enzymatic lignin and alkali lignin.

[0021] By adopting the above technical solution, the present application preferably selects the type of lignin raw material, and among them, enzymatically hydrolyzed lignin is a new type of lignin isolated from the residue of preparing energy such as butanol by microbial enzymatic hydrolysis of corn straw. Compared with traditional alkali lignin and kraft lignin, enzymatically hydrolyzed lignin has multiple active groups and better reactivity, better phenolization effect, improves the promotion effect of phenolic hydroxyl groups on the curing of epoxy resin, and helps to improve the curing rate of epoxy resin plugging materials.

[0022] Preferably, the active hydrogen donor further includes a bisphenol compound, and the bisphenol compound is prepared by the following method: Mix phenol and p-toluenesulfonic acid, heat to melting, add cardanol, continue to increase the heating temperature for reaction, after the reaction is completed, obtain a crude bisphenol product, repeatedly wash the crude bisphenol product with boiling water, and use ferric chloride solution to detect the residue until the ferric chloride solution and the washing residue do not turn purple when mixed, and dehydrate the residue under vacuum to obtain the bisphenol compound.

[0023] By adopting the above technical solution, based on the Friedel-Crafts alkylation reaction, the present application uses cardanol and phenol as reactants to prepare a bisphenol compound. The above bisphenol compound inherits the C15 fatty chain of cardanol and can introduce the C15 fatty chain into the lignin-based phenolic aldehyde amine curing agent, thereby enhancing the flexibility of the epoxy resin by using the C15 fatty chain and improving the plugging effect of the epoxy resin plugging material.

[0024] In a second aspect, the present application provides a preparation method of an underwater fast-curing modified epoxy resin plugging material, adopting the following technical solution.

[0025] A preparation method of an underwater fast-curing modified epoxy resin plugging material includes the following steps: (1) Mix epoxy resin, filler and diluent, and stir evenly to obtain component A; (2) Mix lignin-based phenolic aldehyde amine curing agent, silane coupling agent and curing accelerator to obtain component B; (3) Mix component A and component B to obtain an underwater fast-curing modified epoxy resin plugging material.

[0026] By adopting the above technical solution, the present application separately formulates component A and component B, and then mixes component A and component B to obtain an underwater fast-curing modified epoxy resin plugging material.

[0027] In summary, the present application has the following beneficial effects: 1. This application introduces polyether segments, phenolic aldehyde skeletons, and lignin skeletons through lignin-based phenolic amine curing agents, and promotes the curing of epoxy resins through phenolic hydroxyl groups. The underwater fast-curing modified epoxy resin plugging material of this application can overcome the adverse effects of the underwater environment on the curing effect, and can obtain a cured body with good strength and flexibility, thus overcoming the defects in the related technology and fully meeting the plugging requirements.

[0028] 2. This application prepares lignin-based phenolic amine curing agents through the Mannich reaction. During the reaction process, lignin-based polyphenolic compounds participate in the reaction through the hydrogen atoms at the ortho and para positions of phenolic hydroxyl groups and the α-position of the carbonyl group on the side chain, and combine with amine compounds under the action of aldehyde compounds to obtain lignin-based phenolic amine curing agents.

[0029] 3. This application uses phenol to carry out phenolic treatment on lignin raw materials. The phenolic treatment can further increase the content of phenolic hydroxyl groups on the basis of lignin raw materials, thereby improving the promotion effect of phenolic hydroxyl groups on the curing of epoxy resins and helping to improve the curing rate of epoxy resin plugging materials. Specific Embodiments

[0030] The following further elaborates on this application in conjunction with examples, preparation examples, and comparative examples. The raw materials involved in this application can all be obtained commercially.

[0031] Preparation Example of Lignin-Based Phenolic Amine Curing Agent The following takes Preparation Example 1 as an example for illustration.

[0032] Preparation Example 1 In this preparation example, the active hydrogen donor is a lignin-based polyphenolic compound, the amine compound is composed of triethylenetetramine and polyetheramine mixed in a weight ratio of 3:1, the polyetheramine is a ternary etheramine T5000, the aldehyde compound is formaldehyde, and the weight ratio of the active hydrogen donor, amine compound, and aldehyde compound is 1:2.6:1.4; in the method for preparing lignin-based polyphenolic compounds, the catalyst used is ammonium acetate, and the dosage of the catalyst is 3% of the weight of the lignin raw material. The lignin raw material is selected as alkali lignin.

[0033] The lignin-based polyphenolic compound is prepared according to the following method: At 55°C, 9.5 g of molten phenol and 0.5 g of water are mixed, and then the catalyst and 2 g of lignin raw material are added to obtain a reaction mixture. The reaction mixture is stirred under the condition of constant temperature heating at 140°C. After 2 h, the reaction ends, and it is cooled with 5°C cold water to obtain a crude product. Dioxane is added to the crude product, and then impurities are removed by centrifugation. Anhydrous ether is added to the residue for precipitation, and the lignin-based polyphenolic compound is obtained after freeze-drying.

[0034] This preparation example provides a lignin-based phenolic amine curing agent, which is prepared according to the following method: Mix the active hydrogen donor and the amine compound, stir and preheat the mixture at 55 °C, add the aldehyde compound, then raise the temperature to 95 °C for reflux reaction. After reacting for 2 h, cool it, and dehydrate the product under vacuum to obtain the lignin-based phenolic aldehyde amine curing agent.

[0035] Preparation Example 2 The difference between this preparation example and Preparation Example 1 is that in the method for preparing the lignin-based polyphenol compound, calcium chloride is used as the catalyst.

[0036] Preparation Example 3 The difference between this preparation example and Preparation Example 1 is that in the method for preparing the lignin-based polyphenol compound, aluminum chloride is used as the catalyst.

[0037] Preparation Example 4 The difference between this preparation example and Preparation Example 3 is that in the method for preparing the lignin-based polyphenol compound, the dosage of the catalyst is 4.5% of the weight of the lignin raw material.

[0038] Preparation Example 5 The difference between this preparation example and Preparation Example 3 is that in the method for preparing the lignin-based polyphenol compound, the dosage of the catalyst is 5% of the weight of the lignin raw material.

[0039] Preparation Example 6 The difference between this preparation example and Preparation Example 3 is that in the method for preparing the lignin-based polyphenol compound, the dosage of the catalyst is 5.5% of the weight of the lignin raw material.

[0040] Preparation Example 7 The difference between this preparation example and Preparation Example 6 is that enzymatic hydrolysis lignin is used as the lignin. The enzymatic hydrolysis lignin is the residue from the fermentation of corn straw to produce ethanol and is provided by COFCO Group.

[0041] Preparation Example 8 The difference between this preparation example and Preparation Example 7 is that the active hydrogen donor also includes a bisphenol compound. The weight ratio of the bisphenol compound to the lignin-based polyphenol compound is 1:4. The bisphenol compound is prepared according to the following method: Mix phenol and p-toluenesulfonic acid, heat to melting at 55 °C, then add cardanol. The molar ratio of cardanol to phenol is 3:1, and the molar ratio of p-toluenesulfonic acid to phenol is 1:50. After the addition is completed, continue to raise the heating temperature to 120 °C for reaction. After reacting for 90 min, obtain the bisphenol crude product. Wash the bisphenol crude product repeatedly with boiling water, and use ferric chloride solution to detect the residue after each washing until the ferric chloride solution and the washing residue do not turn purple when mixed. Then, vacuum dehydrate the residue to obtain the bisphenol compound. Example

[0042] Examples 1 - 5 Taking Example 1 as an example for illustration below.

[0043] Example 1 In this example, the filler is lignin fiber with an average diameter of 40 μm and an average length of 1 mm, the diluent is o - tolyl glycidyl ether, and the epoxy resin is composed of epoxy resin E51, epoxy resin DX7160, and epoxy resin Epon1031A70 mixed in a weight ratio of 10:1:1. The lignin - based phenolic amine curing agent is prepared according to the method of Preparation Example 1, the silane coupling agent is bis(triethoxysilyl)ethane, and the curing accelerator is composed of 2 - phenylimidazole and tris(dimethylaminomethyl)phenol mixed in a weight ratio of 1:1.

[0044] This example provides an underwater fast - setting modified epoxy resin leak - plugging material, which is composed of component A and component B mixed in a weight ratio of 3:1. Component A is composed of the following raw materials in parts by weight: 115 g of epoxy resin, 5 g of filler, and 20 g of diluent; Component B is composed of the following raw materials in parts by weight: 60 g of lignin - based phenolic amine curing agent, 1 g of silane coupling agent, and 2 g of curing accelerator.

[0045] This example provides a preparation method of an underwater fast - setting modified epoxy resin leak - plugging material, including the following steps: (1) Mix epoxy resin, filler, and diluent, and obtain component A after stirring evenly; (2) Mix lignin - based phenolic amine curing agent, silane coupling agent, and curing accelerator to obtain component B; (3) Mix component A and component B in a weight ratio of 3:1 to obtain the underwater fast - setting modified epoxy resin leak - plugging material.

[0046] As shown in Table 1, the differences between Examples 1 - 5 mainly lie in the different raw material ratios of component A and component B.

[0047] Table 1 Raw material ratios Examples 5 - 12 As shown in Table 2, the differences between Examples 5 - 12 are that the preparation examples of the lignin - based phenolic amine curing agent are different.

[0048] Table 2 Preparation examples of the lignin - based phenolic amine curing agent Sample Preparation Example Example 5 Preparation Example 1 Example 6 Preparation Example 2 Example 7 Preparation Example 3 Example 8 Preparation Example 4 Example 9 Preparation Example 5 Example 10 Preparation Example 6 Example 11 Preparation Example 7 Example 12 Preparation Example 8 Comparative example Comparative example 1 In this comparative example, the filler is polybutadiene rubber / polymethyl methacrylate core-shell rubber (Huntsman Chemical Corporation, USA), the diluent is benzyl glycidyl ether, and the epoxy resin is composed of epoxy resin E51, epoxy resin DX7160, and epoxy resin Epon1031A70 mixed in a weight ratio of 10:1:1. The curing agent is ZEEPURTM HG-8003T curing agent, the silane coupling agent is bis(triethoxysilyl)ethane, and the curing accelerator is composed of 2-phenylimidazole and tris(dimethylaminomethyl)phenol mixed in a weight ratio of 1:1.

[0049] This comparative example provides an underwater fast-curing modified epoxy resin leak stoppage material, which is composed of component A and component B mixed in a weight ratio of 3:1. Component A is composed of the following raw materials mixed by weight: 120 g of epoxy resin, 5 g of filler, and 20 g of diluent; Component B is composed of the following raw materials mixed by weight: 60 g of curing agent, 1 g of silane coupling agent, and 2 g of curing accelerator.

[0050] This comparative example provides a preparation method for an underwater fast-curing modified epoxy resin leak stoppage material, including the following steps: (1) Mix the epoxy resin, filler, and diluent, and stir evenly to obtain component A; (2) Mix the lignin-based phenolic amine curing agent, silane coupling agent, and curing accelerator to obtain component B; (3) Mix component A and component B in a weight ratio of 3:1 to obtain the underwater fast-curing modified epoxy resin leak stoppage material.

[0051] Comparative Example 2 The difference between this comparative example and Example 1 is that in the method for preparing the lignin-based phenolic amine curing agent, the lignin-based polyphenol compound is replaced by alkali lignin.

[0052] Comparative Example 3 The difference between this comparative example and Example 1 is that the curing agent is ZEEPURTM HG-8003T curing agent.

[0053] Comparative Example 4 The difference between this comparative example and Example 1 is that in the method for preparing the lignin-based phenolic amine curing agent, the polyetheramine is replaced by the same weight of triethylenetetramine.

[0054] Comparative Example 5 The difference between this comparative example and Example 1 is that component A does not include a filler.

[0055] Performance detection test method Referring to the records of "JC / T 1041-2007 Epoxy Resin Grouting Materials for Concrete Cracks", the compressive strength, elongation at break and initial gel time in water of the epoxy resin leak stoppage materials in each example and comparative example were detected, and the results are shown in Table 3.

[0056] Compressive strength: It was determined in accordance with "GB / T 2567—2008 Test Methods for Properties of Resin Castings". A cylinder with a diameter of 10 mm and a height of 25 mm was intercepted as the specimen. After the casting body was placed at a constant temperature for 28 d, a WDW3020 type microcomputer-controlled electronic universal testing machine was used to conduct 5 tests on the compressive strength of the same specimen, and the pressure value under the maximum pressure before the sample broke was recorded, which was the compressive strength.

[0057] Elongation at break: It was determined in accordance with "GB / T 2568—1995 Test Methods for Tensile Properties of Resin Castings".

[0058] Initial gel time in water: Under laboratory standard conditions (temperature (23±2) °C, relative humidity (50±10) %), the A and B components of the slurry were mixed evenly according to a certain mass ratio, poured into a 250 mL glass beaker, and spread evenly. Then, the 250 mL glass beaker containing the slurry was placed into a 3000 mL glass beaker, and water was poured to the 3000 mL scale. The surface of the slurry mixture was touched with a glass rod every 10 min until the "wire drawing" phenomenon occurred. The time elapsed at this time was recorded, and this time was the initial gel time of the epoxy resin leak stoppage material in water. It was accurate to 10 min.

[0059] Table 3 Test Results Combining Examples 1-5 and Comparative Examples 1-3 and Table 3, it can be seen that the compressive strength and elongation at break measured in Examples 1-5 are higher than those in Comparative Examples 1-3, while the initial gel time in water is shorter. This is because in Examples 1-5, phenolic aldehyde skeletons and lignin skeletons were introduced through lignin-based phenolic amine curing agents, and they synergistically improved the strength performance of the epoxy resin cured body with lignin fibers as the filler; the addition of polyetheramine can make the lignin-based phenolic amine curing agent contain polyether chain segments, and the polyether chain segments can effectively improve the flexibility of the epoxy resin, overcoming the defect of poor flexibility of the epoxy resin, thus increasing the elongation at break; the phenolic hydroxyl groups in the lignin-based phenolic amine curing agent can promote the curing of the epoxy resin, so it can show a higher curing rate underwater. However, the curing agents in Comparative Examples 1-2 lack these characteristics, so the above effects cannot be achieved, resulting in poor performance in the above several aspects.

[0060] Combining Example 1 and Comparative Example 4 and referring to Table 3, it can be seen that the elongation at break measured in Comparative Example 4 is relatively low. This is because the lignin-based phenolic amine curing agent in Comparative Example 4 lacks the polyether chain segments provided by polyether amines and cannot sufficiently improve the flexibility of the epoxy resin through the polyether chain segments. Therefore, fracture occurs at a relatively low elongation rate.

[0061] Combining Example 1 and Comparative Example 5 and referring to Table 3, it can be seen that the compressive strength measured in Comparative Example 5 is relatively low. This is because Comparative Example 5 lacks lignin fibers as fillers and cannot sufficiently improve the strength performance through the synergistic effect between lignin fibers, phenolic skeletons, and lignin skeletons.

[0062] Combining Examples 5 - 7 and referring to Table 3, it can be seen that the initial gel time in water measured in Example 7 is relatively short. This is because aluminum chloride, as a strong Lewis acid, can more efficiently promote the phenolation of lignin raw materials, which helps to improve the curing rate of the epoxy resin plugging material.

[0063] Combining Examples 7 - 10 and referring to Table 3, it can be seen that the initial gel time in water measured in Examples 8 - 10 is relatively short. This is because within this range, the catalytic effect of aluminum chloride is good, which can sufficiently increase the content of phenolic hydroxyl groups in the lignin-based phenolic amine curing agent, improve the promotion of phenolic hydroxyl groups on the curing of epoxy resin, and increase the curing rate of the epoxy resin plugging material.

[0064] Combining Example 10 and Example 11 and referring to Table 3, it can be seen that the initial gel time in water measured in Example 11 is relatively short. This is because compared with traditional alkali lignin and kraft lignin, enzymatic hydrolysis lignin has multiple active groups and better reaction activity, better phenolation effect, improves the promotion of phenolic hydroxyl groups on the curing of epoxy resin, and helps to increase the curing rate of the epoxy resin plugging material.

[0065] Combining Example 11 and Example 12 and referring to Table 3, it can be seen that the elongation at break measured in Example 12 is relatively high. This is because the bisphenol compound inherits the C15 fatty chain of cardanol and can introduce the C15 fatty chain into the lignin-based phenolic amine curing agent, thereby enhancing the flexibility of the epoxy resin using the C15 fatty chain and improving the plugging effect of the epoxy resin plugging material.

[0066] The above-mentioned examples are only explanations of this application and do not limit this application. After reading this specification, those skilled in the art can make modifications to the embodiments of this application that do not contribute creatively as needed, but as long as they are within the scope of the claims of this application, they are protected by the patent law.

Claims

1. An underwater fast-curing modified epoxy resin plugging material, characterized in that: The invention comprises component A and component B, wherein component A comprises epoxy resin, filler and diluent, and component B comprises lignin-based phenol amine curing agent, silane coupling agent and curing accelerator; the filler is selected from lignin fiber; the lignin-based phenol amine curing agent is prepared by Mannich reaction of active hydrogen donor, aldehyde compound and amine compound, the active hydrogen donor comprises lignin-based polyphenol compound, and the amine compound comprises polyether amine and triethylenetetramine.

2. The underwater fast-curing modified epoxy resin plugging material according to claim 1, characterized in that: The component A is prepared by mixing the following raw materials in parts by weight: 115-125 parts of epoxy resin, 5-7 parts of filler, and 20-30 parts of diluent.

3. The underwater fast-curing modified epoxy resin plugging material according to claim 1, characterized in that: The B component is prepared by mixing the following raw materials in parts by weight: 60-70 parts of lignin-based phenolic amine curing agent, 1-1.5 parts of silane coupling agent, and 2-3 parts of curing accelerator.

4. The underwater fast-curing modified epoxy resin plugging material according to claim 1, characterized in that: The lignin-based phenolic amine curing agent is prepared according to the following method: The active hydrogen donor and the amine compound are mixed, the mixture is stirred and preheated, and the aldehyde compound is added, and then the temperature is raised and refluxed to react. After the reaction is completed, the product is cooled and vacuum dehydrated to obtain a lignin-based phenolic amine curing agent.

5. The underwater fast-curing modified epoxy resin plugging material according to claim 4, characterized in that: The lignin-based polyphenol compound is prepared according to the following method: The molten phenol and water are mixed, and a catalyst and a lignin raw material are added to obtain a reaction mixture, the reaction mixture is stirred under a constant temperature condition, and after the reaction is completed, it is cooled with cold water to obtain a crude product, dioxane is added to the crude product, and then impurities are removed by centrifugation, anhydrous ether is added to the residue for precipitation, and a lignin-based polyphenol compound is obtained after freeze-drying.

6. The underwater fast-curing modified epoxy resin plugging material according to claim 5, characterized in that: The catalyst is selected from one of aluminum chloride, calcium chloride and ammonium acetate.

7. The underwater fast-curing modified epoxy resin plugging material according to claim 6, characterized in that: The catalyst is aluminum chloride, and the amount of the catalyst used is 4.5-5.5% of the total weight of the lignin raw material.

8. The underwater fast-curing modified epoxy resin plugging material according to claim 5, characterized in that: The lignin raw material is selected from at least one of enzymatic lignin and alkali lignin.

9. The underwater fast-curing modified epoxy resin plugging material according to claim 4, characterized in that: The active hydrogen donor also includes a bisphenol compound, and the bisphenol compound is prepared according to the following method: Phenol and p-toluenesulfonic acid are mixed, heated until melted, and then cardanol is added, and the heating temperature is continuously increased to react. After the reaction is completed, a crude bisphenol product is obtained. The crude bisphenol product is repeatedly washed with boiling water, and the residue is tested with a ferric chloride solution until the ferric chloride solution and the washing residue do not turn purple when mixed, and the residue is vacuum dehydrated to obtain a bisphenol compound.

10. The method for preparing the underwater fast-curing modified epoxy resin plugging material according to any one of claims 1 to 9, characterized in that: The following steps are involved: (1) Mix the epoxy resin, filler and diluent, and stir evenly to obtain component A; (2) mixing a lignin-based phenolic amine curing agent, a silane coupling agent and a curing accelerator to obtain a component B; (3) Component A and component B are mixed to obtain an underwater fast-curing modified epoxy resin plugging material.

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