Modified epoxy resin and preparation method therefor, composition for epoxy resin grouting material, epoxy resin grouting material, preparation method therefor, and use thereof

Abstract

The present invention relates to the technical field of concrete materials. Disclosed are a modified epoxy resin and a preparation method therefor, a composition for an epoxy resin grouting material, an epoxy resin grouting material, a preparation method therefor, and a use thereof. The method for preparing the modified epoxy resin comprises: heating a polyhydroxy compound and an epoxy resin at 80-100ºC in a nitrogen atmosphere in the presence of a catalyst to obtain the modified epoxy resin, wherein the molar ratio of the polyhydroxy compound, the epoxy resin, and the catalyst is 1:1-2:0.05-0.1; the epoxy resin is a bisphenol A epoxy resin; the catalyst is selected from any one of sodium hydroxide, potassium carbonate, and dimethylaniline; and the polyhydroxy compound is selected from at least one of glycerol, ethylene glycol, propylene glycol, glucose, and butylene glycol. The epoxy resin grouting material of the present invention has more excellent toughness and lower viscosity, and good bonding strength and bonding durability with a concrete matrix.

Description

Modified epoxy resins and their preparation methods, compositions for epoxy resin grouting materials, epoxy resin grouting materials and their preparation methods and applications

[0001] Cross-references to related applications

[0002] This application claims the benefit of Chinese Patent Application No. 202510087034.7, filed on January 20, 2025, the contents of which are incorporated herein by reference. Technical Field

[0003] This invention relates to the field of concrete materials technology, specifically to modified epoxy resins and their preparation methods, compositions for epoxy resin grouting materials, epoxy resin grouting materials and their preparation methods and applications. Background Technology

[0004] Concrete plays an irreplaceable role in infrastructure construction, providing a reliable foundation for human habitation, production, and development. However, concrete structures are constantly subjected to coupled loads from rainwater, temperature changes, and vibrations, inevitably leading to defects such as cracks. Moisture in the air, carrying corrosive substances, can more easily penetrate the concrete structure through these channels, causing steel reinforcement corrosion and severely compromising the structural safety.

[0005] Current standards impose strict requirements on the repair of cracks in concrete structures. For example, in the railway industry, Q / CR 802-2020 stipulates that cracks larger than 0.2 mm and cracks smaller than 0.5 mm in ballastless track beds must be repaired with resin. Therefore, the repair of cracks in concrete structures typically employs organic adhesives such as epoxy resin.

[0006] While existing epoxy resins have overcome the drawbacks of high viscosity and low elongation at break through modification, the compatibility of epoxy resins with concrete and the bond durability of epoxy resins remain unresolved. Therefore, using existing grouting materials to repair cracks can easily lead to repair failure.

[0007] Studies have shown that the bonding between epoxy resin and concrete matrix is ​​essentially a result of both mechanical interlocking and chemical bonding (mainly secondary bonds such as hydrogen bonds). The ability of epoxy resin to penetrate concrete directly determines these two effects, while the polarity of epoxy resin is fundamental to its ability to penetrate cement-based materials. Furthermore, to improve the compatibility of the epoxy resin grouting material with the concrete bonding interface, the introduction of inorganic micro / nano materials can enhance interfacial compatibility while simultaneously increasing the toughness of the cured epoxy resin.

[0008] CN108676535A discloses a low-viscosity, tough, tall oil-based epoxy crack repair material, its preparation method, and its application, including bisphenol A epoxy resin (E51), toughening agent oil-based polyurethane prepolymer, reactive diluent, curing agent, modifier, accelerator, and additives; however, this solution has problems such as poor compatibility and poor adhesion durability between the epoxy crack repair material and cement-based materials.

[0009] In summary, there is an urgent need to develop a low-polarity epoxy resin grouting material suitable for long-term and durable concrete bonding and its preparation method. Summary of the Invention

[0010] The purpose of this invention is to overcome the problems of low bonding strength and poor bonding durability between epoxy resin grouting materials and concrete substrates in the prior art.

[0011] To achieve the above objectives, a first aspect of the present invention provides a method for preparing a modified epoxy resin, the method comprising: heating a polyhydroxy compound and an epoxy resin at 80-100°C in a protective atmosphere and in the presence of a catalyst to obtain a modified epoxy resin.

[0012] The molar ratio of the polyhydroxy compound, the epoxy resin, and the catalyst is 1:1-2:0.05-0.1; the epoxy resin is a bisphenol A type epoxy resin; the catalyst is selected from any one of sodium hydroxide, potassium carbonate, and dimethylaniline; the polyhydroxy compound is selected from at least one of glycerol, ethylene glycol, propylene glycol, glucose, and butanediol.

[0013] A second aspect of the present invention provides a modified epoxy resin prepared by the method described in the first aspect.

[0014] A third aspect of the present invention provides a composition for epoxy resin grouting materials, wherein, relative to 100 parts by weight of modified epoxy resin, the content of a first diluent is 20-30 parts by weight, the content of a second diluent is 1-3 parts by weight, the content of a first amine curing agent is 20-40 parts by weight, the content of a second amine curing agent is 5-10 parts by weight, the content of a defoamer is 0.1-0.2 parts by weight, and the content of a filler is 50-100 parts by weight;

[0015] The first amine curing agent is a modified phenolic amine, and the modified phenolic amine has an amine value of 200-500 KOH / g and a viscosity of 1-2 Pa·s at 25°C; the second amine curing agent is a hyperbranched polyamide with an intrinsic viscosity of 0.05-0.3 g / dL; the first diluent is selected from at least one of polypropylene glycol diglycidyl ether, polyethylene oxide diglycidyl ether, 1,4-butanediol diglycidyl ether, and 1,6-hexanediol diglycidyl ether; the second diluent is selected from at least one of ethanol, acetone, and isopropanol.

[0016] The modified epoxy resin is the modified epoxy resin described in the second aspect.

[0017] A fourth aspect of the present invention provides a method for preparing an epoxy resin grouting material, the method comprising:

[0018] (1) The first diluent, the second diluent, and the modified epoxy resin are subjected to a first mixing treatment to obtain mixture I;

[0019] (2) Mixture I, defoamer and filler are subjected to a second mixing treatment to obtain mixture II;

[0020] (3) The mixture II, the first amine curing agent and the second amine curing agent are subjected to a third mixing treatment to obtain epoxy resin grouting material;

[0021] Relative to every 100 parts by weight of the modified epoxy resin, the content of the first diluent is 20-30 parts by weight, the content of the second diluent is 1-3 parts by weight, the content of the first amine curing agent is 20-40 parts by weight, the content of the second amine curing agent is 5-10 parts by weight, the content of the defoamer is 0.1-0.2 parts by weight, and the content of the filler is 50-100 parts by weight;

[0022] The first amine curing agent is a modified phenolic amine, and the modified phenolic amine has an amine value of 200-500 KOH / g and a viscosity of 1-2 Pa·s at 25°C; the second amine curing agent is a hyperbranched polyamide with an intrinsic viscosity of 0.05-0.3 g / dL; the first diluent is selected from at least one of polypropylene glycol diglycidyl ether, polyethylene oxide diglycidyl ether, 1,4-butanediol diglycidyl ether, and 1,6-hexanediol diglycidyl ether; the second diluent is selected from at least one of ethanol, acetone, and isopropanol.

[0023] The modified epoxy resin is the modified epoxy resin described in the second aspect.

[0024] The fifth aspect of the present invention provides an epoxy resin grouting material prepared by the method described in the fourth aspect.

[0025] The sixth aspect of the present invention provides the application of the epoxy resin grouting material described in the fifth aspect in concrete.

[0026] The present invention has at least the following advantages:

[0027] (1) The epoxy resin grouting material of the present invention has low polarity, which can better wet the concrete matrix and further enhance the bonding strength with the concrete matrix under the action of mechanical interlocking and chemical bonding.

[0028] (2) The epoxy resin grouting material of the present invention has good toughness and low viscosity.

[0029] (3) The epoxy resin grouting material of the present invention can effectively increase the wetting performance of the epoxy resin grouting material on the water-covered concrete matrix by changing the surface structure of the water-covered layer at the interface of concrete cracks, and effectively solve the problem of poor affinity between epoxy resin grouting material and water.

[0030] (4) The epoxy resin grouting material of the present invention has the advantage of good bonding durability. Detailed Implementation

[0031] The endpoints and any values ​​of the ranges disclosed herein are not limited to the precise ranges or values, and these ranges or values ​​should be understood to include values ​​close to these ranges or values. For numerical ranges, the endpoint values ​​of the various ranges, the endpoint values ​​of the various ranges and individual point values, and individual point values ​​can be combined with each other to obtain one or more new numerical ranges, which should be considered as specifically disclosed herein.

[0032] The solid-liquid mass ratio mentioned in this invention is the mass ratio of solid to liquid.

[0033] As mentioned above, a first aspect of the present invention provides a method for preparing a modified epoxy resin, the method comprising: heating a polyhydroxy compound and an epoxy resin at 80-100°C in a protective atmosphere and in the presence of a catalyst to obtain a modified epoxy resin.

[0034] The molar ratio of the polyhydroxy compound, the epoxy resin, and the catalyst is 1:1-2:0.05-0.1; the epoxy resin is a bisphenol A type epoxy resin; the catalyst is selected from any one of sodium hydroxide, potassium carbonate, and dimethylaniline; the polyhydroxy compound is selected from at least one of glycerol, ethylene glycol, propylene glycol, glucose, and butanediol.

[0035] Preferably, the bisphenol A type epoxy resin is E51 type epoxy resin and / or E44 type epoxy resin. The inventors of this invention have discovered that, under these preferred conditions, the epoxy resin grouting material of this invention exhibits superior toughness and lower viscosity, as well as good bond strength and durability with the concrete matrix.

[0036] Preferably, the conditions for the heat treatment include: a time of 6-12 hours and a stirring speed of 500-1000 rpm.

[0037] As previously stated, a second aspect of the present invention provides a modified epoxy resin prepared by the method described in the first aspect.

[0038] Preferably, the modified epoxy resin has an epoxy value of 0.2-0.3. The inventors of this invention have discovered that, under these preferred conditions, the epoxy resin grouting material of this invention exhibits superior toughness and lower viscosity, as well as good bond strength and durability with the concrete matrix.

[0039] Preferably, the protective atmosphere is nitrogen.

[0040] As previously described, a third aspect of the present invention provides a composition for epoxy resin grouting materials, wherein, relative to 100 parts by weight of modified epoxy resin, the content of a first diluent is 20-30 parts by weight, the content of a second diluent is 1-3 parts by weight, the content of a first amine curing agent is 20-40 parts by weight, the content of a second amine curing agent is 5-10 parts by weight, the content of a defoamer is 0.1-0.2 parts by weight, and the content of a filler is 50-100 parts by weight;

[0041] The first amine curing agent is a modified phenolic amine, and the modified phenolic amine has an amine value of 200-500 KOH / g and a viscosity of 1-2 Pa·s at 25°C; the second amine curing agent is a hyperbranched polyamide with an intrinsic viscosity of 0.05-0.3 g / dL; the first diluent is selected from at least one of polypropylene glycol diglycidyl ether, polyethylene oxide diglycidyl ether, 1,4-butanediol diglycidyl ether, and 1,6-hexanediol diglycidyl ether; the second diluent is selected from at least one of ethanol, acetone, and isopropanol.

[0042] The modified epoxy resin is the modified epoxy resin described in the second aspect.

[0043] According to a particularly preferred embodiment, the hyperbranched polyamide is prepared by a method comprising:

[0044] (1) Sodium hydroxide solution and aminoacetic acid are mixed to obtain solution I; and solution I and 3,5-dinitrobenzoyl chloride are subjected to a first reaction, and sodium hydroxide solution is added dropwise during the first reaction to maintain the reaction pH at 8-9 throughout the first reaction to obtain substance I; the conditions for the first reaction include: time of 15-25 min;

[0045] (2) Acidify the substance I with dilute hydrochloric acid to obtain substance II; and recrystallize the substance II to obtain substance III;

[0046] (3) Subject the substance III to a self-condensation reaction to obtain the hyperbranched polyamide; the conditions for the self-condensation reaction include: under a nitrogen atmosphere, at a temperature of 150-160°C, for a time of 4-5 h.

[0047] The inventors of this invention have discovered that, under these preferred conditions, the epoxy resin grouting material of this invention has superior toughness and lower viscosity, and good bonding strength and durability with the concrete matrix.

[0048] Preferably, the hyperbranched polyamide has an intrinsic viscosity of 0.2-0.25 g / dL and a molecular weight of 3-4 kg / mol. The inventors of this invention have discovered that, under these preferred conditions, the epoxy resin grouting material of this invention exhibits superior toughness and lower viscosity, as well as good bond strength and durability with the concrete matrix.

[0049] Preferably, the defoamer is a polyether-type defoamer.

[0050] Preferably, the average particle diameter of the filler is <50μm.

[0051] More preferably, the filler is selected from at least one of cement, limestone powder, amorphous hydrated calcium silicate, quartz powder, slag, ceramic powder, fly ash, silica fume, silica, precipitated silica and talc.

[0052] In a preferred embodiment, the filler is selected from amorphous hydrated calcium silicate. The inventors of this invention have discovered that, under these preferred conditions, the epoxy resin grouting material of this invention exhibits superior toughness.

[0053] According to a particularly preferred embodiment, the amorphous hydrated calcium silicate is prepared by a method comprising: subjecting calcium oxide and nano-silica to a hydrothermal reaction, wherein the mass ratio of calcium oxide to nano-silica is 1:0.8-1.2, and ensuring that the solid-liquid mass ratio is 1:8-12 at the start of the reaction; the hydrothermal reaction conditions include a temperature of 75-85°C and a time of 7-9 hours. The inventors of this invention have found that, under these preferred conditions, the epoxy resin grouting material of this invention exhibits superior toughness and lower viscosity, and good bonding strength and durability with the concrete matrix.

[0054] It should be noted that the first amine curing agent in this invention also includes: ethylenediamine, diethylenetriamine, triethylenetetramine, triethanolamine, tetraethylenepentamine, diallyltriamine, and triethylenediamine. However, the inventors of this invention have discovered that when the first amine curing agent is a modified phenolic amine, in combination with the other components in this invention, the prepared epoxy resin grouting material has better toughness and lower viscosity, and better bonding strength and bonding durability with the concrete matrix.

[0055] As previously described, a fourth aspect of the present invention provides a method for preparing an epoxy resin grouting material, the method comprising:

[0056] (1) The first diluent, the second diluent, and the modified epoxy resin are subjected to a first mixing treatment to obtain mixture I;

[0057] (2) Mixture I, defoamer and filler are subjected to a second mixing treatment to obtain mixture II;

[0058] (3) The mixture II, the first amine curing agent and the second amine curing agent are subjected to a third mixing treatment to obtain epoxy resin grouting material;

[0059] Relative to every 100 parts by weight of the modified epoxy resin, the amount of the first diluent is 20-30 parts by weight, the amount of the second diluent is 1-3 parts by weight, the amount of the first amine curing agent is 20-40 parts by weight, the amount of the second amine curing agent is 5-10 parts by weight, the amount of the defoamer is 0.1-0.2 parts by weight, and the amount of the filler is 50-100 parts by weight.

[0060] The first amine curing agent is a modified phenolic amine, and the modified phenolic amine has an amine value of 200-500 KOH / g and a viscosity of 1-2 Pa·s at 25°C; the second amine curing agent is a hyperbranched polyamide with an intrinsic viscosity of 0.05-0.3 g / dL; the first diluent is selected from at least one of polypropylene glycol diglycidyl ether, polyethylene oxide diglycidyl ether, 1,4-butanediol diglycidyl ether, and 1,6-hexanediol diglycidyl ether; the second diluent is selected from at least one of ethanol, acetone, and isopropanol.

[0061] The modified epoxy resin is the modified epoxy resin described in the second aspect.

[0062] This invention does not particularly limit the methods for the first mixing, the second mixing, and the third mixing. Those skilled in the art can select methods according to conventional methods, and this should not be construed as a limitation of the invention. Exemplarily, the conditions for the first mixing include: a stirring speed of 100-200 rpm and a time of 1-2 min; the conditions for the second mixing include: a stirring speed of 50-100 rpm and a time of 1-2 min; and the conditions for the third mixing include: a stirring speed of 100-200 rpm and a time of 1-2 min.

[0063] As previously described, the fifth aspect of the present invention provides an epoxy resin grouting material prepared by the method described in the fourth aspect.

[0064] As previously stated, the sixth aspect of the present invention provides the application of the epoxy resin grouting material described in the fifth aspect in concrete.

[0065] The present invention will be described in detail below through examples. Unless otherwise specified, the instruments, reagents, and materials involved in the following examples are all conventional instruments, reagents, and materials that can be obtained through legitimate commercial channels.

[0066] DGEBA epoxy resin: Phoenix brand E51, purchased from Shandong Yousuo Chemical Technology Co., Ltd.

[0067] Modified phenolic amine: amine value 300KOH / g, viscosity at 25℃ 1.2Pa·s, model T31, purchased from Changzhou Runxiang Chemical Co., Ltd.

[0068] Polyether-type defoamer: Model ZJ-D130, purchased from Jiangsu Zhaojia Building Materials Technology Co., Ltd.

[0069] The average particle diameter of the filler is 15 μm.

[0070] In this invention, each part by weight represents 10g.

[0071] The molecular weight of the hyperbranched polyamide in this invention was tested by gel permeation chromatography, wherein the mobile phase was chromatographic grade THF (tetrahydrofuran).

[0072] The intrinsic viscosity of the hyperbranched polyamide in this invention represents the ratio of specific viscosity to solution concentration at the limiting concentration in a dilute solution, and is tested according to GB / T 1632 standard.

[0073] Fly ash: specific surface area 427 m² 2 / kg, loss on ignition 1.7wt%, purchased from Changde Power Generation Co., Ltd.

[0074] Preparations 1 to 3 were used to prepare modified epoxy resins:

[0075] Preparation Example 1

[0076] In a nitrogen atmosphere, glycerol (a polyhydroxy compound, specifically 1 mol), DGEBA epoxy resin (epoxy resin), and dimethylaniline (catalyst) in a molar ratio of 1:1:0.05 were heated at 100°C and a stirring speed of 500 rpm for 6 h to obtain a modified epoxy resin with an epoxy value of 0.29, named G1.

[0077] Preparation Example 2

[0078] In a nitrogen atmosphere, 1 mol of glycerol (a polyhydroxy compound, specifically 1 mol), DGEBA epoxy resin (epoxy resin), and dimethylaniline (catalyst) in a molar ratio of 1:1:0.05 were heated at 150°C and a stirring speed of 500 rpm for 6 h to obtain a modified epoxy resin with an epoxy value of 0.22, named G2.

[0079] Preparation Example 3

[0080] In a nitrogen atmosphere, 1 mol of glycerol (a polyhydroxy compound, specifically 1 mol), DGEBA epoxy resin (epoxy resin), and dimethylaniline (catalyst) in a molar ratio of 1:3:0.01 were heated at 100°C and a stirring speed of 500 rpm for 6 h to obtain a modified epoxy resin with an epoxy value of 0.36, named G3.

[0081] Preparation Examples 4 to 6 were used to prepare hyperbranched polyamides:

[0082] Preparation Example 4

[0083] (1) Mix 20 mL of 1 g / mol sodium hydroxide solution and 3.0 g of aminoacetic acid to obtain solution I; and carry out a first reaction with 9.2 g of 3,5-dinitrobenzoyl chloride, and maintain the reaction pH at 8.5 throughout the first reaction by adding sodium hydroxide solution dropwise to obtain substance I; the conditions for the first reaction include: time of 20 min;

[0084] (2) Acidify the substance I with dilute hydrochloric acid to obtain substance II; and recrystallize the substance II to obtain substance III; the acidification time is 10 min;

[0085] (3) Subject the substance III to a self-condensation reaction to obtain the hyperbranched polyamide; the conditions for the self-condensation reaction include: under a nitrogen atmosphere, at a temperature of 160°C, for a time of 4 hours.

[0086] The hyperbranched polyamide is named hyperbranched polyamide I, as detailed in Table 1.

[0087] Preparation Example 5

[0088] (1) Mix 20 mL of 1 g / mol sodium hydroxide solution and 3.0 g of aminoacetic acid to obtain solution I; and carry out a first reaction with 9.2 g of 3,5-dinitrobenzoyl chloride, and maintain the reaction pH at 8.5 throughout the first reaction by adding sodium hydroxide solution dropwise to obtain substance I; the conditions for the first reaction include: time of 20 min, and controlling the pH of the first reaction at 8.5;

[0089] (2) Acidify the substance I with dilute hydrochloric acid to obtain substance II; and recrystallize the substance II to obtain substance III; the acidification time is 10 min;

[0090] (3) Subject the substance III to a self-condensation reaction to obtain the hyperbranched polyamide; the conditions for the self-condensation reaction include: under a nitrogen atmosphere, at a temperature of 160°C, for a time of 5 hours.

[0091] The hyperbranched polyamide is named hyperbranched polyamide II, as detailed in Table 1.

[0092] Preparation Example 6

[0093] (1) Mix 20 mL of 1 g / mol sodium hydroxide solution and 3.0 g of aminoacetic acid to obtain solution I; and carry out a first reaction with 9.2 g of 3,5-dinitrobenzoyl chloride, and maintain the reaction pH at 8.5 throughout the first reaction by adding sodium hydroxide solution dropwise to obtain substance I; the conditions for the first reaction include: time of 20 min, and controlling the pH of the first reaction at 8.5;

[0094] (2) Acidify the substance I with dilute hydrochloric acid to obtain substance II; and recrystallize the substance II to obtain substance III; the acidification time is 10 min;

[0095] (3) Subject the substance III to a self-condensation reaction to obtain the hyperbranched polyamide; the conditions for the self-condensation reaction include: under a nitrogen atmosphere, at a temperature of 160°C, for a time of 6 hours.

[0096] The hyperbranched polyamide is named hyperbranched polyamide III, as detailed in Table 1.

[0097] Table 1

[0098] Preparation Example 7 was used to prepare amorphous hydrated calcium silicate:

[0099] Preparation Example 7

[0100] Calcium oxide and nano-silica in a mass ratio of 1:1 were subjected to a hydrothermal reaction with water, ensuring that the solid-liquid mass ratio was 1:10 at the beginning of the hydrothermal reaction. The conditions for the hydrothermal reaction included a temperature of 80°C and a time of 8 hours, resulting in amorphous hydrated calcium silicate.

[0101] Example 1

[0102] (1) 1,4-Butanediol diglycidyl ether (first diluent), acetone (second diluent) and G1 (modified epoxy resin) were mixed for 2 min at a stirring speed of 200 rpm to obtain mixture I;

[0103] (2) Mixture I, polyether-type defoamer (defoamer) and amorphous hydrated calcium silicate (filler) are subjected to a second mixing treatment for 2 minutes at a stirring speed of 100 rpm to obtain mixture II;

[0104] (3) The mixture II, modified phenolic amine (first amine curing agent) and hyperbranched polyamide (second amine curing agent) are subjected to a third mixing treatment for 2 minutes at a stirring speed of 200 rpm to obtain epoxy resin grouting material, named Z1.

[0105] Example 2

[0106] This embodiment uses a similar process to Embodiment 1, except that the amount of G1 is different. The rest is the same as in Embodiment 1. The epoxy resin grouting material is prepared and named Z2. See Table 2 for details.

[0107] Example 3

[0108] This embodiment uses a similar process to Embodiment 1, except that the amount of 1,4-butanediol diglycidyl ether is different. The rest is the same as in Embodiment 1. The epoxy resin grouting material is prepared and named Z3. See Table 2 for details.

[0109] Example 4

[0110] This embodiment uses a similar process to Embodiment 1, except that the amount of acetone used is different. The rest is the same as in Embodiment 1. The epoxy resin grouting material is prepared and named Z4. See Table 2 for details.

[0111] Example 5

[0112] This embodiment uses a similar process to Embodiment 1, except that the amount of filler used is different. The rest is the same as in Embodiment 1. The epoxy resin grouting material is prepared and named Z5. See Table 2 for details.

[0113] Example 6

[0114] This embodiment uses a similar process to Embodiment 1, except that the amount of modified phenolic amine used is different. The rest is the same as in Embodiment 1. The epoxy resin grouting material is prepared and named Z6. See Table 2 for details.

[0115] Example 7

[0116] This embodiment uses a similar process to Embodiment 1, except that the amount of hyperbranched polyamide used is different. The rest is the same as in Embodiment 1. The epoxy resin grouting material is prepared and named Z7. See Table 2 for details.

[0117] Example 8

[0118] This embodiment uses a similar process to Embodiment 1, except that the type of hyperbranched polyamide is different. Otherwise, it is the same as Embodiment 1. The epoxy resin grouting material is prepared and named Z8. See Table 2 for details.

[0119] Example 9

[0120] This embodiment uses a similar process to Embodiment 1, except that amorphous hydrated calcium silicate is replaced with fly ash of equal weight and particle size. The rest is the same as in Embodiment 1. An epoxy resin grouting material named Z9 is prepared. See Table 2 for details.

[0121] Comparative Example 1

[0122] This comparative example uses a similar process to Example 1, except that G1 is replaced with an equal amount of DGEBA epoxy resin. The rest is the same as in Example 1. The resulting epoxy resin grouting material is named DZ1. See Table 3 for details.

[0123] Comparative Example 2

[0124] This comparative example uses a similar process to Example 1, except that 1,4-butanediol diglycidyl ether (the first diluent) is not added. Otherwise, it is the same as Example 1. The resulting epoxy resin grouting material is named DZ2. See Table 3 for details.

[0125] Comparative Example 3

[0126] This comparative example uses a similar process to Example 1, except that acetone (the second diluent) is not added. Otherwise, it is the same as Example 1. The resulting epoxy resin grouting material is named DZ3. See Table 3 for details.

[0127] Comparative Example 4

[0128] This comparative example uses a similar process to Example 1, except that amorphous hydrated calcium silicate (filler) is not added. Otherwise, it is the same as Example 1. The resulting epoxy resin grouting material is named DZ4. See Table 3 for details.

[0129] Comparative Example 5

[0130] This comparative example uses a similar process to Example 1, except that the type of the second amine curing agent is different. The rest is the same as in Example 1. An epoxy resin grouting material was prepared and named DZ5. See Table 3 for details.

[0131] Comparative Example 6

[0132] This comparative example uses a similar process to Example 1, except that G1 is replaced with an equal amount of G2. The rest is the same as in Example 1. An epoxy resin grouting material named DZ6 is prepared. See Table 3 for details.

[0133] Comparative Example 7

[0134] This comparative example uses a similar process to Example 1, except that G1 is replaced with an equal amount of G3. The rest is the same as in Example 1. The resulting epoxy resin grouting material is named DZ7. See Table 3 for details.

[0135] Comparative Example 8

[0136] This comparative example uses a similar process to Example 1, except that the amount of each component is different. The rest is the same as in Example 1. The resulting epoxy resin grouting material is named DZ8. See Table 3 for details.

[0137] Table 2

[0138] Continued from Table 2

[0139] Table 3

[0140] Continued from Table 3

[0141] Test case

[0142] Test on bond-flexural strength (i.e., bond strength between epoxy resin grouting material and concrete matrix) after concrete crack repair:

[0143] A 100mm×100mm×400mm cement mortar sample, cured for 28 days, was cut using a machine tool. Two cut cement mortar samples were placed 1mm apart to simulate cracks. The two sides (the two sides perpendicular to the ground) of the two cut cement mortar samples, with a 1mm gap, were sealed with aluminum tape, leaving a grouting opening on the upper surface. The epoxy resin grouting materials prepared in Examples 1 to 9 and Comparative Examples 1 to 8 were injected into the cracks. After 7 days of epoxy resin grouting, the tape was removed, and the sample was cut to obtain cut sample A. It was ensured that the epoxy resin grouting material in cut sample A was sandwiched in the middle of the cement mortar, and the dimensions of cut sample A were 40mm*40mm*160mm. The interfacial flexural strength of cut sample A was then tested. This method ensures that there is no excess epoxy resin grouting material on the cement mortar surface, ensuring the accuracy of the test results.

[0144] In the dry bond flexural strength test, the cut surface of the 100mm×100mm×400mm cement mortar sample needs to be air-dried at room temperature for one day before the epoxy resin grout is poured in. In the wet bond flexural strength test, the cut surface of the 100mm×100mm×400mm cement mortar sample needs to be soaked in water for one day, then the surface water is wiped off before the epoxy resin grout is poured in. The bond durability test involves placing a 40mm*40mm*160mm cut sample A in water for 28 days, 56 days, and 112 days before testing the bond flexural strength.

[0145] After the cut specimen A was left to stand at room temperature for 24 hours, the bond flexural strength test was conducted at a loading rate of 50 N / s. Each group of tests was performed three times, and the average value of the three flexural strength results was taken. The specific results are shown in Table 4. This test method is based on the literature Yuan et al., Comparative study of reactive diluents with different molecular structures on the curing properties of epoxy adhesives and the interface bonding properties with mortar, International Journal of Adhesion and Adhesives, 126(2023)103473.

[0146] Viscosity and toughness testing of epoxy resin grouting materials

[0147] The viscosity of the epoxy resin grouting materials prepared in Examples 1 to 9 and Comparative Examples 1 to 8 was measured using an NDJ-9S digital rotational viscometer (Shanghai Lichen Bangxi Instrument Technology Co., Ltd.) according to the standard "Plastics - Resins in the liquid state or as emulsions or dispersions - Determination of apparent viscosity using a single cylinder type rotational viscometer method" ISO 2555:2018(E). The results are the average of six measurements. The loading speed of the universal testing machine was 2 mm / min. When testing tensile specimens, a displacement extensometer was installed in the working section to continuously detect displacement changes. The test results are shown in Table 5.

[0148] The toughness of epoxy resin grouting material at 7 days after curing was determined according to standard GB / T 2567-2008 "Test Methods for Performance of Resin Castings", and expressed as elongation at break. The test results are shown in Table 5.

[0149] Table 4

[0150] Table 5

[0151] As can be seen from the results in Tables 4 and 5, the epoxy resin grouting material prepared by the present invention has better toughness and lower viscosity, and good bonding strength and bonding durability with the concrete matrix.

[0152] The preferred embodiments of the present invention have been described in detail above; however, the present invention is not limited thereto. Within the scope of the inventive concept, various simple modifications can be made to the technical solutions of the present invention, including combinations of various technical features in any other suitable manner. These simple modifications and combinations should also be considered as the content disclosed in the present invention and are all within the protection scope of the present invention.

Claims

1. A composition for epoxy resin grouting material, characterized in that, In this composition, relative to every 100 parts by weight of modified epoxy resin, the content of the first diluent is 20-30 parts by weight, the content of the second diluent is 1-3 parts by weight, the content of the first amine curing agent is 20-40 parts by weight, the content of the second amine curing agent is 5-10 parts by weight, the content of the defoamer is 0.1-0.2 parts by weight, and the content of the filler is 50-100 parts by weight; The first amine curing agent is a modified phenolic amine, and the modified phenolic amine has an amine value of 200-500 KOH / g and a viscosity of 1-2 Pa·s at 25°C; the second amine curing agent is a hyperbranched polyamide with an intrinsic viscosity of 0.05-0.3 g / dL; the first diluent is selected from at least one of polypropylene glycol diglycidyl ether, polyethylene oxide diglycidyl ether, 1,4-butanediol diglycidyl ether, and 1,6-hexanediol diglycidyl ether; the second diluent is selected from at least one of ethanol, acetone, and isopropanol. The average particle diameter of the filler is <50μm; The method for preparing the modified epoxy resin includes: heating a polyhydroxy compound and an epoxy resin at 80-100°C in a protective atmosphere and in the presence of a catalyst to obtain the modified epoxy resin. The molar ratio of the polyhydroxy compound, the epoxy resin, and the catalyst is 1:1-2:0.05-0.1; the epoxy resin is a bisphenol A type epoxy resin; the catalyst is selected from any one of sodium hydroxide, potassium carbonate, and dimethylaniline; the polyhydroxy compound is selected from at least one of glycerol, ethylene glycol, propylene glycol, glucose, and butanediol.

2. The composition according to claim 1, characterized in that, The bisphenol A type epoxy resin is E51 type epoxy resin and / or E44 type epoxy resin.

3. The composition according to claim 1 or 2, characterized in that, The conditions for the heat treatment include: a time of 6-12 hours and a stirring speed of 500-1000 rpm.

4. The composition according to claim 1 or 2, characterized in that, The hyperbranched polyamide has an intrinsic viscosity of 0.2-0.25 g / dL and a molecular weight of 3-4 kg / mol.

5. A method for preparing epoxy resin grouting material, characterized in that, The method includes: (1) The first diluent, the second diluent, and the modified epoxy resin are subjected to a first mixing treatment to obtain mixture I; (2) Mixture I, defoamer and filler are subjected to a second mixing treatment to obtain mixture II; (3) The mixture II, the first amine curing agent and the second amine curing agent are subjected to a third mixing treatment to obtain epoxy resin grouting material; Relative to every 100 parts by weight of the modified epoxy resin, the amount of the first diluent is 20-30 parts by weight, the amount of the second diluent is 1-3 parts by weight, the amount of the first amine curing agent is 20-40 parts by weight, the amount of the second amine curing agent is 5-10 parts by weight, the amount of the defoamer is 0.1-0.2 parts by weight, and the amount of the filler is 50-100 parts by weight. The first amine curing agent is a modified phenolic amine, and the modified phenolic amine has an amine value of 200-500 KOH / g and a viscosity of 1-2 Pa·s at 25°C; the second amine curing agent is a hyperbranched polyamide with an intrinsic viscosity of 0.05-0.3 g / dL; the first diluent is selected from at least one of polypropylene glycol diglycidyl ether, polyethylene oxide diglycidyl ether, 1,4-butanediol diglycidyl ether, and 1,6-hexanediol diglycidyl ether; the second diluent is selected from at least one of ethanol, acetone, and isopropanol; the average particle diameter of the filler is <50 μm.

6. The epoxy resin grouting material prepared by the method of claim 5.

7. The application of the epoxy resin grouting material according to claim 6 in concrete.

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