Epoxy mastic patching compound, method of making and use thereof

Abstract

The application discloses an epoxy mortar repairing agent and a preparation method and application thereof. The epoxy mortar repairing agent comprises components A, B and C in a mass ratio of 100:20-40:20-40. The component A comprises the following components in a weight ratio: biomimetic hardening filler 20-50 parts, epoxy resin 30-50 parts and dispersing agent 0.2-1 part. The component B comprises the following components in a weight ratio: polysulfane curing agent 30-60 parts, amine curing agent 30-60 parts and accelerator 1-3 parts. The component C comprises the following components in a weight ratio: branched polysiloxane 20-50 parts and drainage wetting agent 20-50 parts. The epoxy mortar repairing agent has the characteristics of pressure and water construction, high strength, fast curing and strong adhesion, and can be applied to the fields of pressure and water repairing and water reinforcing of various engineering equipment and facilities.

Description

Technical Field

[0001] This invention relates to the field of underwater construction protection, specifically to an epoxy putty repair agent, its preparation method, and its application. Background Technology

[0002] Modern large-scale petrochemical companies primarily rely on underground or underwater metal fiber pipelines to transport oil, gas, and water. These pipelines are prone to damage during long-term use due to corrosion, erosion, vibration, seasonal changes, and underground variations, leading to leaks of the transported media. If pipelines are not repaired promptly, leaks worsen, polluting the environment; offline repairs require shutting down the pipeline, increasing processing time, and delaying production. Existing wet repair materials mainly include cement-based materials, polyurethane-based materials, and epoxy resin-based materials. Cement-based materials have weak adhesion and incomplete underwater curing; polyurethane-based materials contain a large number of isocyanate groups that are sensitive to water, resulting in a violent reaction and making application difficult in wet conditions; epoxy resin-based materials allow for controlled reaction rates through adjustable curing agent systems, facilitating underwater construction. Currently, most wet repair materials are based on epoxy resin, combined with a high proportion of fillers and hydrophobic components to create high-viscosity, hydrophobic repair materials. This allows for the removal of water from the substrate surface and rapid curing into a repair. However, existing epoxy-based repair materials require offline pressure cessation during use, and their curing is slow and incomplete when repairing under water, making them unsuitable for repairing under pressure and water. Therefore, developing a repair agent capable of performing repairs under pressure and water conditions is of great significance. Summary of the Invention

[0003] To address the problems of existing pipe repair agents, such as inability to be used under pressure and slow and incomplete curing under water, the primary objective of this invention is to provide an epoxy mortar repair agent. Because branched polysiloxanes react rapidly with amine curing agents, and drainage wetting agents react with epoxy resins and polythiol curing agents, the epoxy mortar repair agent formulation of this invention is divided into components A, B, and C. The epoxy mortar repair agent prepared by this invention features pressurized application, rapid curing under water, strong adhesion, high wear resistance, and environmental friendliness.

[0004] The second objective of this invention is to provide a method for preparing an epoxy putty repair agent. The epoxy putty repair agent provided by this invention utilizes biomimetic hardening fillers to modify its morphology. Its unique monomer structure endows the repair agent with strong resistance to disturbance, high bulk strength, high wear resistance, and high adhesion. Therefore, the repair agent can remain undeformed under high-pressure water flow impact, achieving pressure-bearing repair, and exhibits high adhesion and good wear resistance after curing. The epoxy putty repair agent provided by this invention uses a drainage wetting agent to achieve water-bearing adhesion, and its unique monomer structure endows the repair agent with high wetting and strong adhesion functions. The epoxy putty repair agent of this invention can strongly wet the substrate surface regardless of water, achieving strong adhesion even when wet. The epoxy resin and polythiol curing agent used in the epoxy putty repair agent provided by this invention react with an amine curing agent to form a main cross-linked network, providing the main function for the high adhesion of the repair agent. However, the curing reaction is slow and highly susceptible to water influence. Therefore, the epoxy mortar repair agent provided by this invention uses branched polysiloxane as a rapid curing agent. Its unique monomer structure gives the curing agent high functional density, high hydrophobicity, and rapid curing capabilities, thus ensuring that the curing process of the repair agent is unaffected by water and achieving water-based curing repair. This repair agent overcomes the technical difficulties of existing pipe repair agents, such as their inability to be used under pressure and water, slow curing, and incomplete curing. It can be applied to the bonding and repair of pipe leaks or engineering facilities in low-temperature, humid, or underwater environments.

[0005] A third objective of this invention is to provide an application of an epoxy putty repair agent.

[0006] The primary objective of this invention can be achieved through the following technical solution:

[0007] An epoxy putty repair agent, comprising component A, component B, and component C in a mass ratio of 100:20-40:20-40;

[0008] Component A comprises the following components in parts by weight:

[0009] Bionic hardening filler 20-50

[0010] Epoxy resin 30-50

[0011] Dispersant 0.2-1;

[0012] Component B comprises the following components in parts by weight:

[0013] Polythiol curing agent 30-60

[0014] Amine curing agents 30-60

[0015] Accelerators 1-3;

[0016] Component C comprises the following components in parts by weight:

[0017] Branched polysiloxane 20-50

[0018] Drainage wetting agent 20-50.

[0019] Preferably, the biomimetic hardening filler in component A is prepared by surface modification of at least one of silicon carbide, basalt fiber, silica, quartz powder, barite powder, alumina, and kaolin with silane coupling agent (KH570) and dopamine hydrochloride.

[0020] The biomimetic hardening filler is prepared by the following steps.

[0021] Step 1: Using anhydrous ethanol as a solvent, take 5-10 parts by weight of silane coupling agent (KH570) and prepare a 1% by weight mixed solution in the reactor. Then, add 80-100 parts by weight of at least one of silicon carbide, basalt fiber, silica, quartz powder, barite powder, alumina, and kaolin mixed in any proportion to the reactor and stir at 50-80°C for 6-10 hours. Then wash with anhydrous ethanol and dry for 12 hours to obtain surface-modified hardened filler.

[0022] Step 2: Prepare a Tris-HCl buffer solution with pH=7.5 in the reactor. Add 5-10 parts by weight of dopamine hydrochloride and 80-100 parts by weight of surface-modified hardening filler to the buffer solution. Stir for 24 hours, filter, dry and grind evenly to obtain the biomimetic hardening filler.

[0023] Preferably, the epoxy resin in component A is a bisphenol A type epoxy resin with an epoxy equivalent of 180-200 g / eq or a bisphenol F type epoxy resin with an epoxy equivalent of 168-182 g / eq.

[0024] Preferably, the dispersant in component A is at least one of the following: Deqian 9250, Deqian 904S, BASF 4010, BASF 4310, BASF 5065, and BYK 163, mixed in any proportion.

[0025] Preferably, the polythiol curing agent in component B is at least one of pentaerythritol tetra(mercaptoacetic acid), 2,3-dithio(2-mercapto)-1-propanethiol, 1,4-benzenedithiol, trimethylolpropane tri(mercaptoacetic acid), trimethylolpropane tri(3-mercaptopropionate), pentaerythritol tetra(3-mercaptopropionic acid), and dipentaerythritol hexa(3-mercaptopropionic acid).

[0026] Preferably, the amine curing agent in component B is at least one of isophorone diamine, pyrimidine-4,5,6-triamine, 4H-1,2,4-triazole-3,4,5-triamine, triethylenetetramine, tetraethylenepentamine, diethylenetriamine, and diethyltoluenediamine, mixed in any proportion.

[0027] Preferably, the accelerator in component B is at least one of nonylphenol NP, N-isopropyl-N-methyltert-butylamine, triethylamine, 2-methylimidazole, and 2,4,6-tris(dimethylaminomethyl)phenol, mixed in any proportion.

[0028] Preferably, the branched polysiloxane in component C is prepared by hydrolysis and condensation of at least two of the following: tetraethyl silicate and dimethoxydiphenylsilane, tris(trimethsiloxy)silane, trimethoxymethsilane, dimethoxy(methyl)silane, methyltrimethoxysilane, propyltrimethoxysilane, octyltrimethoxysilane, chlorotriethoxysilane, phenyltriethoxysilane, decyltrimethoxysilane, and methyltriethoxysilane.

[0029] The branched polysiloxane is prepared by the following steps:

[0030] Step 1: Add at least two of the following to the reactor: tetraethyl silicate and dimethoxydiphenylsilane, tris(trimethoxysilane), trimethoxymethsilane, dimethoxy(methyl)silane, methyltrimethoxysilane, propyltrimethoxysilane, octyltrimethoxysilane, chlorotriethoxysilane, phenyltriethoxysilane, decyltrimethoxysilane, and methyltriethoxysilane. The tetraethyl silicate accounts for 20% to 80% of the total mass of silane. Add at least one of methanol, ethanol, and isopropanol mixed in any proportion, with a mass percentage of 30% to 60%, and stir until homogeneous.

[0031] Step 2: Under stirring at 50-80℃, add 1-3 parts hydrochloric acid and 10-20 parts deionized water to the mixture obtained in Step 1, and maintain the polymerization reaction at 50-80℃ for 12-24 hours.

[0032] Step 3: After cooling the mixture obtained in Step 2 to room temperature, distill it under reduced pressure at 60-100°C to remove water, catalyst and alcohol solvent from the reactor to obtain branched polysiloxane.

[0033] Preferably, the water-draining wetting agent in component C is prepared by hydrolysis and condensation of at least two of the following: propyltriethoxysilane isocyanate, dimethoxydiphenylsilane, tris(trimethsiloxy)silane, trimethoxymethylsilane, dimethoxy(methyl)silane, methyltrimethoxysilane, propyltrimethoxysilane, octyltrimethoxysilane, chlorotriethoxysilane, phenyltriethoxysilane, decyltrimethoxysilane, and methyltriethoxysilane.

[0034] The drainage wetting agent is prepared by the following steps:

[0035] Step 1: Add at least two of the following to the reactor: propyltriethoxysilane and dimethoxydiphenylsilane, tris(trimethsiloxy)silane, trimethoxymethsilane, dimethoxy(methyl)silane, methyltrimethoxysilane, propyltrimethoxysilane, octyltrimethoxysilane, chlorotriethoxysilane, phenyltriethoxysilane, decyltrimethoxysilane, and methyltriethoxysilane. The propyltriethoxysilane comprises 20% to 80% of the total mass of silane. Add 30% to 60% by mass of at least one of methanol, ethanol, and isopropanol mixed in any proportion, and stir until homogeneous.

[0036] Step 2: Under stirring at 50-80℃, add 1-3 parts hydrochloric acid and 10-20 parts deionized water to the mixture obtained in Step 1, and maintain the polymerization reaction at 50-80℃ for 12-24 hours.

[0037] Step 3: After cooling the mixture obtained in Step 2 to room temperature, distill it under reduced pressure at 60-100°C to remove water, catalyst and alcohol solvent from the reactor to obtain a water-removing wetting agent.

[0038] The second objective of this invention can be achieved through the following technical solution:

[0039] A method for preparing an epoxy putty repair agent includes the following steps:

[0040] (1) Mix 20-50 parts of biomimetic hardening filler, 30-50 parts of epoxy resin, and 0.2-1 parts of dispersant to obtain component A;

[0041] (2) Mix 30-60 parts of polythiol curing agent, 30-60 parts of amine curing agent and 1-3 parts of accelerator to obtain component B;

[0042] (3) Mix 20-50 parts of branched polysiloxane and 20-50 parts of drainage wetting agent to obtain component C;

[0043] (4) Mix components A, B and C in a mass ratio of 100:20-40:20-40 to obtain epoxy putty repair agent.

[0044] The third objective of this invention can be achieved through the following technical solution:

[0045] Application of an epoxy putty repair agent in emergency repair of pipeline leaks under pressure and water.

[0046] The present invention has the following advantages and beneficial effects compared with existing materials:

[0047] The epoxy putty adhesive of this invention uses a biomimetic rigid filler with high hardness, which can significantly improve the bulk strength and wear resistance of the repair agent. The catechol structure in the biomimetic rigid filler can enhance the adhesion of the repair agent. At the same time, the secondary amine groups in the biomimetic rigid filler react with epoxy resin, and the addition of a large amount gives the repair agent extremely high viscosity, thereby giving the repair agent excellent anti-disturbance properties, allowing the repair agent to resist the impact of high-pressure water flow without dispersing, and realizing the function of pressure repair.

[0048] The drainage and wetting agent used in this invention contains a high density of isocyanate groups and siloxane groups. First, the hydrophobic alkyl groups enhance the underwater wettability of the epoxy putty repair agent, removing most of the moisture from the substrate surface. Then, the isocyanate groups react with water, consuming the small amount of bound water on the substrate surface. Simultaneously, the reaction releases carbon dioxide, shielding the boundary water layer around the repair agent and transforming the water / repair agent interface into a water / air / repair agent interface. Through the synergistic effect of these two processes, the repair agent rapidly wets the substrate surface, replacing the water / substrate interface with the repair agent / substrate interface, thus improving the adhesion between the repair agent and the substrate. The products of the hydrolysis of the siloxane groups can react with the hydroxyl groups on the substrate surface to form new chemical bonds, further enhancing the adhesion of the repair agent.

[0049] The epoxy putty adhesive of the present invention uses branched polysiloxane as a fast curing agent. It has a branched structure and contains a large amount of uncondensed silanol. After being mixed with amine curing agent, it can undergo a rapid condensation reaction to form a cross-linked network, achieve a certain degree of curing, shield against the intrusion of moisture, protect the epoxy-thiol and epoxy-amine reactions to proceed smoothly, and achieve short-term water-resistant repair function. Attached Figure Description

[0050] Figure 1 This is a demonstration of the morphology of the epoxy putty repair agent in Example 4;

[0051] Figure 2 This is a demonstration of the pressurized and wet repair process of epoxy putty repair agent in Example 4. Detailed Implementation

[0052] The present invention will be further described in detail below with reference to specific embodiments, but the implementation of the present invention is not limited thereto. All materials used in the examples of the present invention are commercially available.

[0053] Example 1

[0054] (1) Using anhydrous ethanol as a solvent, 5 parts by mass of KH570 were prepared into a 1% mixed solution in a reactor. Then, 80 parts by mass of kaolin and barite powder were added to the reactor at a mass ratio of 1:1. The mixture was stirred at 50-80℃ for 6-10 hours. Then, it was washed with anhydrous ethanol and dried for 12 hours to obtain the surface-modified hardened filler.

[0055] (2) Prepare a Tris-HCl buffer solution with pH=7.5 in the reactor. Add 8 parts by mass of dopamine hydrochloride and 90 parts by mass of surface-modified hardening filler to the buffer solution. Stir for 24 hours, filter, dry and grind evenly to obtain biomimetic hardening filler.

[0056] (3) 79 parts of tetraethyl silicate, 20 parts by weight of tris(trimethylsiloxy)silane, 15 parts of anhydrous ethanol, 5 parts of deionized water and 1 part of concentrated hydrochloric acid were added to a reaction vessel and heated and stirred at 60°C for 10 h. The hydrochloric acid, ethanol and water in the system were removed by vacuum distillation at 80°C to obtain branched polysiloxane.

[0057] (4) Add 45 parts by weight of propyltriethoxysilane isocyanate, 65 parts by weight of tris(trimethylsiloxy)silane, 12 parts of anhydrous ethanol, 6 parts of deionized water and 1 part of concentrated hydrochloric acid into a reaction vessel, heat and stir at 60°C for 7 hours, and remove hydrochloric acid, ethanol and water from the system by vacuum distillation at 70°C to obtain a water-draining wetting agent.

[0058] (5) Mix 30 parts of biomimetic hardening filler, 50 parts of bisphenol A epoxy resin and 0.2 parts of Deqian 9250 to obtain component A;

[0059] (6) Mix 50 parts by weight of pentaerythritol tetra(3-mercaptopropionic acid) ester, 50 parts by weight of isophorone diamine and 1 part by weight of nonylphenol NP to obtain component B.

[0060] (7) Mix 20 parts of branched polysiloxane and 40 parts of drainage wetting agent to obtain component C;

[0061] (8) Weigh components A, B, and C in a mass ratio of 100:30:20. Mix components A and B thoroughly, then add component C and mix thoroughly to obtain epoxy putty repair agent.

[0062] Example 2

[0063] (1) Using anhydrous ethanol as a solvent, 7 parts by mass of KH570 were prepared into a 1% mixed solution in a reactor. Then, 85 parts by mass of kaolin and quartz powder were added to the reactor at a mass ratio of 1:1. The mixture was stirred at 50-80℃ for 6-10 hours. Then, it was washed with anhydrous ethanol and dried for 12 hours to obtain the surface-modified hardened filler.

[0064] (2) Prepare a Tris-HCl buffer solution with pH=7.5 in the reactor. Add 8 parts by mass of dopamine hydrochloride and 90 parts by mass of surface-modified hardening filler to the buffer solution. Stir for 24 hours, filter, dry and grind evenly to obtain biomimetic hardening filler.

[0065] (3) 79 parts of tetraethyl silicate, 20 parts by weight of methyltrimethoxysilane, 15 parts of anhydrous ethanol, 5 parts of deionized water and 1 part of concentrated hydrochloric acid were added to a reaction vessel and heated and stirred at 60°C for 10 h. The hydrochloric acid, ethanol and water in the system were removed by vacuum distillation at 80°C to obtain branched polysiloxane.

[0066] (4) Add 45 parts by weight of propyltriethoxysilane isocyanate, 65 parts by weight of methyltrimethoxysilane, 12 parts of anhydrous ethanol, 6 parts of deionized water and 1 part of concentrated hydrochloric acid into a reaction vessel, heat and stir at 60°C for 7 hours, and remove hydrochloric acid, ethanol and water from the system by vacuum distillation at 70°C to obtain a water-draining wetting agent.

[0067] (5) Mix 40 parts by weight of biomimetic hardening filler, 50 parts by weight of bisphenol A epoxy resin and 0.6 parts by weight of Deqian 904S to obtain component A;

[0068] (6) Mix 35 parts by weight of 2,3-dithio(2-mercapto)-1-propanethiol, 35 parts by weight of pyrimidine-4,5,6-triamine, and 3 parts by weight of N-isopropyl-N-methyl tert-butylamine to obtain component B.

[0069] (7) Mix 33 parts of branched polysiloxane and 28 parts of drainage wetting agent to obtain component C;

[0070] (8) Weigh components A, B, and C in a mass ratio of 100:20:30. Mix components A and B thoroughly, then add component C and mix thoroughly to obtain epoxy putty repair agent.

[0071] Example 3

[0072] (1) Using anhydrous ethanol as a solvent, 6 parts by mass of KH570 were prepared into a 1% mixed solution in a reactor. Then, 85 parts by mass of basalt fiber and quartz powder were added to the reactor at a mass ratio of 1:1. The mixture was stirred at 50-80℃ for 6-10 hours. Then, it was washed with anhydrous ethanol and dried for 12 hours to obtain the surface-modified hardened filler.

[0073] (2) Prepare a Tris-HCl buffer solution with pH=7.5 in the reactor. Add 8 parts by mass of dopamine hydrochloride and 90 parts by mass of surface-modified hardening filler to the buffer solution. Stir for 24 hours, filter, dry and grind evenly to obtain biomimetic hardening filler.

[0074] (3) 79 parts of tetraethyl silicate, 20 parts by weight of octyltrimethoxysilane, 15 parts of anhydrous ethanol, 5 parts of deionized water and 1 part of concentrated hydrochloric acid were added to a reaction vessel and heated and stirred at 60°C for 10 h. The hydrochloric acid, ethanol and water in the system were removed by vacuum distillation at 80°C to obtain branched polysiloxane.

[0075] (4) Add 45 parts by weight of propyltriethoxysilane isocyanate, 65 parts by weight of octyltrimethoxysilane, 12 parts of anhydrous ethanol, 6 parts of deionized water and 1 part of concentrated hydrochloric acid into a reaction vessel, heat and stir at 60°C for 7 hours, and remove hydrochloric acid, ethanol and water from the system by vacuum distillation at 70°C to obtain a water-draining wetting agent.

[0076] (5) Mix 33 parts by weight of biomimetic hardening filler, 47 parts by weight of bisphenol F epoxy resin and 1 part by weight of BASF 4010 to obtain component A.

[0077] (6) Mix 28 parts by weight of 1,4-benzenedithiol, 28 parts by weight of triethylenetetramine and 3 parts by weight of 2-methylimidazole to obtain component B;

[0078] (7) Mix 23 parts of branched polysiloxane and 24 parts of drainage wetting agent to obtain component C;

[0079] (8) Weigh components A, B, and C in a mass ratio of 100:33:22. Mix components A and B thoroughly, then add component C and mix thoroughly to obtain the epoxy putty repair agent.

[0080] Example 4

[0081] (1) Using anhydrous ethanol as a solvent, 8 parts by mass of KH570 were prepared into a 1% mixed solution in a reactor. Then, 8 parts by mass of basalt fiber and alumina were added to the reactor at a mass ratio of 1:1. The mixture was stirred at 50-80℃ for 6-10 hours. Then, it was washed with anhydrous ethanol and dried for 12 hours to obtain the surface-modified hardened filler.

[0082] (2) Prepare a Tris-HCl buffer solution with pH=7.5 in the reactor. Add 8 parts by mass of dopamine hydrochloride and 90 parts by mass of surface-modified hardening filler to the buffer solution. Stir for 24 hours, filter, dry and grind evenly to obtain biomimetic hardening filler.

[0083] (3) 79 parts of tetraethyl silicate, 20 parts by weight of phenyltriethoxysilane, 15 parts of anhydrous ethanol, 5 parts of deionized water and 1 part of concentrated hydrochloric acid were added to a reaction vessel and heated and stirred at 60°C for 10 h. The hydrochloric acid, ethanol and water in the system were removed by vacuum distillation at 80°C to obtain branched polysiloxane.

[0084] (4) Add 45 parts by weight of propyltriethoxysilane isocyanate, 65 parts by weight of phenyltriethoxysilane, 12 parts of anhydrous ethanol, 6 parts of deionized water and 1 part of concentrated hydrochloric acid into a reaction vessel, heat and stir at 60°C for 7 hours, and remove hydrochloric acid, ethanol and water from the system by vacuum distillation at 70°C to obtain a water-draining wetting agent.

[0085] (5) Mix 30 parts by weight of biomimetic hardening filler, 40 parts by weight of bisphenol A epoxy resin and 0.5 parts by weight of BASF 5065 to obtain component A;

[0086] (6) Mix 45 parts by weight of pentaerythritol tetra(3-mercaptopropionic acid) ester, 45 parts by weight of diethylenetriamine and 2 parts by weight of 2-methylimidazole to obtain component B.

[0087] (7) Mix 30 parts of branched polysiloxane and 27 parts of drainage wetting agent to obtain component C;

[0088] (8) Weigh components A, B, and C in a mass ratio of 100:30:40. Mix components A and B thoroughly, then add component C and mix thoroughly to obtain epoxy putty repair agent.

[0089] Comparative Example 1

[0090] (1) Using anhydrous ethanol as a solvent, 8 parts by mass of KH570 were prepared into a 1% mixed solution in a reactor. Then, 90 parts by mass of basalt fiber and alumina were added to the reactor at a mass ratio of 1:1. The mixture was stirred at 50-80℃ for 6-10 hours. Then, it was washed with anhydrous ethanol and dried for 12 hours to obtain the surface-modified hardened filler.

[0091] (2) Prepare a Tris-HCl buffer solution with pH=7.5 in the reactor. Add 8 parts by mass of dopamine hydrochloride and 90 parts by mass of surface-modified hardening filler to the buffer solution. Stir for 24 hours, filter, dry and grind evenly to obtain biomimetic hardening filler.

[0092] (3) Mix 30 parts by weight of biomimetic hardening filler, 40 parts by weight of bisphenol A epoxy resin and 0.5 parts by weight of BASF 5065 to obtain component A;

[0093] (4) Mix 45 parts by weight of pentaerythritol tetra(3-mercaptopropionic acid) ester, 45 parts by weight of diethylenetriamine and 2 parts by weight of 2-methylimidazole to obtain component B.

[0094] (5) Mix components A and B at a mass ratio of 100:30 to obtain epoxy putty repair agent.

[0095] Comparative Example 2

[0096] (1) Add 45 parts by weight of propyltriethoxysilane isocyanate, 65 parts by weight of phenyltriethoxysilane, 12 parts of anhydrous ethanol, 6 parts of deionized water and 1 part of concentrated hydrochloric acid into a reaction vessel, heat and stir at 60°C for 7 hours, and remove hydrochloric acid, ethanol and water from the system by vacuum distillation at 70°C to obtain a water-draining wetting agent.

[0097] (2) Mix 40 parts by weight of bisphenol A type epoxy resin and 0.5 parts by weight of BASF 5065 to obtain component A;

[0098] (3) Mix 45 parts by weight of pentaerythritol tetra(3-mercaptopropionic acid) ester, 45 parts by weight of diethylenetriamine and 2 parts by weight of 2-methylimidazole to obtain component B.

[0099] (4) Component C consists of 27 parts of drainage and wetting agent;

[0100] (5) Weigh components A, B, and C in a mass ratio of 100:30:40. Mix components A and B thoroughly, then add component C and mix thoroughly to obtain epoxy putty repair agent.

[0101] Comparative Example 3

[0102] (1) 79 parts of tetraethyl silicate, 20 parts by weight of phenyltriethoxysilane, 15 parts of anhydrous ethanol, 5 parts of deionized water and 1 part of concentrated hydrochloric acid were added to a reaction vessel and heated and stirred at 60°C for 10 h. The hydrochloric acid, ethanol and water in the system were removed by vacuum distillation at 80°C to obtain branched polysiloxane.

[0103] (2) Mix 40 parts by weight of bisphenol A type epoxy resin and 0.5 parts by weight of BASF 5065 to obtain component A;

[0104] (3) Mix 45 parts by weight of pentaerythritol tetra(3-mercaptopropionic acid) ester, 45 parts by weight of diethylenetriamine and 2 parts by weight of 2-methylimidazole to obtain component B.

[0105] (4) Component C contains 30 parts of branched polysiloxane;

[0106] (5) Weigh components A, B, and C in a mass ratio of 100:30:40. Mix components A and B thoroughly, then add component C and mix thoroughly to obtain epoxy putty repair agent.

[0107] Comparative Example 4

[0108] (1) Using anhydrous ethanol as a solvent, 8 parts by mass of KH570 were prepared into a 1% mixed solution in a reactor. Then, 90 parts by mass of basalt fiber and alumina were added to the reactor at a mass ratio of 1:1. The mixture was stirred at 50-80℃ for 6-10 hours. Then, it was washed with anhydrous ethanol and dried for 12 hours to obtain the surface-modified hardened filler.

[0109] (2) Prepare a Tris-HCl buffer solution with pH=7.5 in the reactor. Add 8 parts by mass of dopamine hydrochloride and 90 parts by mass of surface-modified hardening filler to the buffer solution. Stir for 24 hours, filter, dry and grind evenly to obtain biomimetic hardening filler.

[0110] (3) Add 45 parts by weight of propyltriethoxysilane isocyanate, 65 parts by weight of phenyltriethoxysilane, 12 parts of anhydrous ethanol, 6 parts of deionized water and 1 part of concentrated hydrochloric acid into a reaction vessel, heat and stir at 60°C for 7 hours, and remove hydrochloric acid, ethanol and water from the system by vacuum distillation at 70°C to obtain a water-draining wetting agent.

[0111] (4) Mix 30 parts by weight of biomimetic hardening filler, 40 parts by weight of bisphenol A epoxy resin and 0.5 parts by weight of BASF 5065 to obtain component A;

[0112] (5) Mix 45 parts by weight of pentaerythritol tetra(3-mercaptopropionic acid) ester, 45 parts by weight of diethylenetriamine and 2 parts by weight of 2-methylimidazole to obtain component B.

[0113] (6) Component C contains 30 parts of branched polysiloxane;

[0114] (7) Weigh components A, B, and C in a mass ratio of 100:30:40. Mix components A and B thoroughly, then add component C and mix thoroughly to obtain epoxy putty repair agent.

[0115] Comparative Example 5

[0116] (1) Using anhydrous ethanol as a solvent, 8 parts by mass of KH570 were prepared into a 1% mixed solution in a reactor. Then, 90 parts by mass of basalt fiber and alumina were added to the reactor at a mass ratio of 1:1. The mixture was stirred at 50-80℃ for 6-10 hours. Then, it was washed with anhydrous ethanol and dried for 12 hours to obtain the surface-modified hardened filler.

[0117] (2) Prepare a Tris-HCl buffer solution with pH=7.5 in the reactor. Add 8 parts by mass of dopamine hydrochloride and 90 parts by mass of surface-modified hardening filler to the buffer solution. Stir for 24 hours, filter, dry and grind evenly to obtain biomimetic hardening filler.

[0118] (3) 79 parts of tetraethyl silicate, 20 parts by weight of phenyltriethoxysilane, 15 parts of anhydrous ethanol, 5 parts of deionized water and 1 part of concentrated hydrochloric acid were added to a reaction vessel and heated and stirred at 60°C for 10 h. The hydrochloric acid, ethanol and water in the system were removed by vacuum distillation at 80°C to obtain branched polysiloxane.

[0119] (5) Mix 30 parts by weight of biomimetic hardening filler, 40 parts by weight of bisphenol A epoxy resin and 0.5 parts by weight of BASF 5065 to obtain component A;

[0120] (6) Mix 45 parts by weight of pentaerythritol tetra(3-mercaptopropionic acid) ester, 45 parts by weight of diethylenetriamine and 2 parts by weight of 2-methylimidazole to obtain component B.

[0121] (7) Component C contains 27 parts of a drainage wetting agent;

[0122] (8) Weigh components A, B, and C in a mass ratio of 100:30:40. Mix components A and B thoroughly, then add component C and mix thoroughly to obtain epoxy putty repair agent.

[0123] Comparative Example 6

[0124] (1) 79 parts of tetraethyl silicate, 20 parts by weight of phenyltriethoxysilane, 15 parts of anhydrous ethanol, 5 parts of deionized water and 1 part of concentrated hydrochloric acid were added to a reaction vessel and heated and stirred at 60°C for 10 h. The hydrochloric acid, ethanol and water in the system were removed by vacuum distillation at 80°C to obtain branched polysiloxane.

[0125] (2) Add 45 parts by weight of propyltriethoxysilane isocyanate, 65 parts by weight of phenyltriethoxysilane, 12 parts of anhydrous ethanol, 6 parts of deionized water and 1 part of concentrated hydrochloric acid into a reaction vessel, heat and stir at 60°C for 7 hours, and remove hydrochloric acid, ethanol and water from the system by vacuum distillation at 70°C to obtain a water-draining wetting agent.

[0126] (3) Mix 40 parts by weight of bisphenol A type epoxy resin and 0.5 parts by weight of BASF 5065 to obtain component A;

[0127] (4) Mix 45 parts by weight of pentaerythritol tetra(3-mercaptopropionic acid) ester, 45 parts by weight of diethylenetriamine and 2 parts by weight of 2-methylimidazole to obtain component B.

[0128] (5) Mix 30 parts of branched polysiloxane and 27 parts of drainage wetting agent to obtain component C;

[0129] (6) Weigh components A, B, and C in a mass ratio of 100:30:40. Mix components A and B thoroughly, then add component C and mix thoroughly to obtain epoxy putty repair agent.

[0130] Performance testing

[0131]

[0132] (1) Refer to GB / T 2411-2008

[0133] (2) Refer to GB / T 5478-2008, CS-17, load 1000g, 1000rad, 60r / min

[0134] (3) Refer to GB / T 2567-2021

[0135] (4) Refer to GB / T 2567-2021

[0136] (5) Refer to GB / T 5210-2006

[0137] (6) Refer to GB / T 12007.7-1989

[0138] (7) The method for testing the anti-disturbance stability is as follows: use a high-pressure water gun to rinse 30g of epoxy putty repair agent for 60s, record the mass before and after rinsing, and calculate the anti-disturbance stability according to Formula 1. The rinsing pressure is 0.1MPa.

[0139]

[0140] The performance test results show that, compared with Comparative Examples 1-6, the epoxy mortar repair agent prepared in Example 4 of this invention exhibits significantly improved performance, including increased Shore hardness, compressive strength, tensile strength, and adhesion, and decreased abrasion value and gel time. Compared with Comparative Example 6, Example 4 shows significantly improved abrasion resistance, mainly due to the high hardness of the released hardening filler and its good compatibility with the resin curing agent components. Compared with Comparative Example 5, Example 4 shows significantly improved adhesion, as the drainage wetting agent can react and break down the interfacial water layer, improving the wettability between the epoxy mortar repair agent and the substrate. Compared with Comparative Example 4, Example 4 shows significantly improved curing speed, because the branched siloxane can rapidly dehydrate and condense into a highly cross-linked body, accelerating the curing process of the epoxy mortar repair agent.

[0141] The above embodiments are preferred embodiments of the present invention, but the embodiments of the present invention are not limited to the above embodiments. Any changes, modifications, substitutions, combinations, or simplifications made without departing from the spirit and principle of the present invention shall be considered equivalent substitutions and shall be included within the protection scope of the present invention.

Claims

1. An epoxy putty repair agent, characterized in that, Includes components A, B, and C with a mass ratio of 100:20~40:20~40; Component A comprises the following components in parts by weight: Bionic hardening filler 20~50 Epoxy resin 30~50 Dispersant 0.2~1; Component B comprises the following components in parts by weight: Polythiol curing agent 30~60 Amine curing agent 30~60 Accelerator 1~3; Component C comprises the following components in parts by weight: Branched polysiloxane 20~50 Drainage wetting agent 20~50; The biomimetic hardening filler in component A is prepared by surface modification of at least one of silicon carbide, basalt fiber, silica, quartz powder, barite powder, alumina, and kaolin with silane coupling agent and dopamine hydrochloride. The biomimetic hardening filler is prepared by the following steps. Step 1: Using anhydrous ethanol as a solvent, prepare a 1% (by mass) mixed solution of 5-10 parts by mass of silane coupling agent in a reactor. Then, add at least one of the following in any proportion: silicon carbide, basalt fiber, silica, quartz powder, barite powder, alumina, and kaolin to the reactor and stir at 50-80°C for 6-10 hours. Then, wash with anhydrous ethanol and dry for 12 hours to obtain the surface-modified hardened filler. Step 2: Prepare a Tris-HCl buffer solution with pH=7.5 in the reactor. Add 5-10 parts by weight of dopamine hydrochloride and 80-100 parts by weight of surface-modified hardening filler to the buffer solution. Stir for 24 hours, filter, dry and grind evenly to obtain the biomimetic hardening filler. The branched polysiloxane in component C is prepared by hydrolysis and condensation of at least two of the following: tetraethyl silicate and dimethoxydiphenylsilane, tris(trimethsiloxy)silane, trimethoxymethylsilane, dimethoxy(methyl)silane, methyltrimethoxysilane, propyltrimethoxysilane, octyltrimethoxysilane, chlorotriethoxysilane, phenyltriethoxysilane, decyltrimethoxysilane, and methyltriethoxysilane. The branched polysiloxane is prepared by the following steps: Step 1: Add at least two of the following to the reactor: tetraethyl silicate and dimethoxydiphenylsilane, tris(trimethoxysilane), trimethoxymethsilane, dimethoxy(methyl)silane, methyltrimethoxysilane, propyltrimethoxysilane, octyltrimethoxysilane, chlorotriethoxysilane, phenyltriethoxysilane, decyltrimethoxysilane, and methyltriethoxysilane. The tetraethyl silicate accounts for 20% to 80% of the total mass of silane. Add at least one of methanol, ethanol, and isopropanol mixed in any proportion, with a mass percentage of 30% to 60%, and stir until homogeneous. Step 2: Under stirring at 50-80℃, add 1-3 parts hydrochloric acid and 10-20 parts deionized water to the mixture obtained in Step 1, and maintain the polymerization reaction at 50-80℃ for 12-24 h. Step 3: After cooling the mixture obtained in Step 2 to room temperature, distill it under reduced pressure at 60~100℃ to remove water, catalyst and alcohol solvent from the reactor to obtain branched polysiloxane. The water-draining and wetting agent in component C is prepared by hydrolysis and condensation of at least two of the following: propyltriethoxysilane isocyanate, dimethoxydiphenylsilane, tris(trimethsiloxy)silane, trimethoxymethylsilane, dimethoxy(methyl)silane, methyltrimethoxysilane, propyltrimethoxysilane, octyltrimethoxysilane, chlorotriethoxysilane, phenyltriethoxysilane, decyltrimethoxysilane, and methyltriethoxysilane. The drainage wetting agent is prepared by the following steps: Step 1: Add at least two of the following to the reactor: propyltriethoxysilane and dimethoxydiphenylsilane, tris(trimethsiloxy)silane, trimethoxymethsilane, dimethoxy(methyl)silane, methyltrimethoxysilane, propyltrimethoxysilane, octyltrimethoxysilane, chlorotriethoxysilane, phenyltriethoxysilane, decyltrimethoxysilane, and methyltriethoxysilane. The propyltriethoxysilane comprises 20% to 80% of the total mass of silane. Add 30% to 60% by mass of at least one of methanol, ethanol, and isopropanol mixed in any proportion, and stir until homogeneous. Step 2: Under stirring at 50-80℃, add 1-3 parts hydrochloric acid and 10-20 parts deionized water to the mixture obtained in Step 1, and maintain the polymerization reaction at 50-80℃ for 12-24 h. Step 3: After cooling the mixture obtained in Step 2 to room temperature, distill it under reduced pressure at 60~100℃ to remove water, catalyst and alcohol solvent from the reactor to obtain a water-removing wetting agent.

2. The epoxy putty repair agent according to claim 1, characterized in that, The epoxy resin in component A is a bisphenol A type epoxy resin with an epoxy equivalent of 180~200 g / eq or a bisphenol F type epoxy resin with an epoxy equivalent of 168~182 g / eq; the dispersant in component A is at least one of Deqian 9250, Deqian 904S, BASF 4010, BASF 4310, BASF 5065, and BYK 163 mixed in any proportion.

3. The epoxy putty repair agent according to claim 1, characterized in that, The polythiol curing agent in component B is at least one of the following: pentaerythritol tetra(mercaptoacetic acid) ester, 2,3-dithio(2-mercapto)-1-propanethiol, 1,4-benzenedithiol, trimethylolpropane tri(mercaptoacetic acid), trimethylolpropane tri(3-mercaptopropionate), pentaerythritol tetra(3-mercaptopropionic acid) ester, and dipentaerythritol hexa(3-mercaptopropionic acid) ester, mixed in any proportion.

4. The epoxy putty repair agent according to claim 1, characterized in that, The amine curing agent in component B is at least one of the following: isophorone diamine, pyrimidine-4,5,6-triamine, 4H-1,2,4-triazole-3,4,5-triamine, triethylenetetramine, tetraethylenepentamine, diethylenetriamine, and diethyltoluenediamine, mixed in any proportion.

5. The epoxy putty repair agent according to claim 1, characterized in that, The accelerator in component B is at least one of nonylphenol NP, N-isopropyl-N-methyl tert-butylamine, triethylamine, 2-methylimidazole, and 2,4,6-tris(dimethylaminomethyl)phenol, mixed in any proportion.

6. A method for preparing an epoxy putty repair agent according to any one of claims 1 to 5, comprising the following steps: (1) Mix 20-50 parts of biomimetic hardening filler, 30-50 parts of epoxy resin, and 0.2-1 parts of dispersant to obtain component A; (2) Mix 30-60 parts of polythiol curing agent, 30-60 parts of amine curing agent, and 1-3 parts of accelerator to obtain component B; (3) Mix 20-50 parts of branched polysiloxane and 20-50 parts of drainage wetting agent to obtain component C; (4) Mix components A, B and C in a mass ratio of 100:20~40:20~40 to obtain epoxy putty repair agent.

7. The application of an epoxy mortar repair agent according to any one of claims 1 to 5 in the emergency repair of pipeline leaks under pressure and water.

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