CN114933782B - Epoxy resin grouting material and preparation method thereof - Google Patents

Epoxy resin grouting material and preparation method thereof Download PDF

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CN114933782B
CN114933782B CN202210494468.5A CN202210494468A CN114933782B CN 114933782 B CN114933782 B CN 114933782B CN 202210494468 A CN202210494468 A CN 202210494468A CN 114933782 B CN114933782 B CN 114933782B
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epoxy resin
parts
grouting material
acid
carboxyl
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CN114933782A (en
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元强
王攒
姚灏
余志武
李光均
王欢
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Central South University
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/14—Polycondensates modified by chemical after-treatment
    • C08G59/1433—Polycondensates modified by chemical after-treatment with organic low-molecular-weight compounds
    • C08G59/1438—Polycondensates modified by chemical after-treatment with organic low-molecular-weight compounds containing oxygen
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C08K2003/2206—Oxides; Hydroxides of metals of calcium, strontium or barium
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
    • Y02W30/00—Technologies for solid waste management
    • Y02W30/50—Reuse, recycling or recovery technologies
    • Y02W30/91—Use of waste materials as fillers for mortars or concrete

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  • Chemical & Material Sciences (AREA)
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  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Emergency Medicine (AREA)
  • General Chemical & Material Sciences (AREA)
  • Sealing Material Composition (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Adhesives Or Adhesive Processes (AREA)
  • Epoxy Resins (AREA)

Abstract

The invention provides an epoxy resin grouting material which comprises the following raw material components in parts by mass: 100 parts of carboxyl-terminated modified epoxy resin, 20-40 parts of curing agent, 5-10 parts of toughening agent, 2-3 parts of coupling agent, 2-5 parts of thixotropic agent, 5-10 parts of water-absorbing filler, 15-20 parts of hydrophilic diluent and 10-15 parts of aliphatic reactive diluent; the carboxyl-terminated modified epoxy resin is dicarboxylic acid modified anionic hydrophilic epoxy resin, and the epoxy value of the epoxy resin is 0.25-0.30. The invention also provides a preparation method of the epoxy resin grouting material, which comprises the steps of S1, preparing the carboxyl-terminated modified epoxy resin; s2, preparing a premix; and S3, preparing the epoxy resin grouting material. The epoxy resin grouting material prepared by the invention can realize good grouting and bonding effects on a concrete crack interface in a humid environment.

Description

Epoxy resin grouting material and preparation method thereof
Technical Field
The invention relates to the technical field of building materials, in particular to an epoxy resin grouting material for concrete cracks in a humid environment and a preparation method thereof.
Background
The concrete is prepared by mixing a cementing material, cement, sand, aggregate, water and an additive according to a certain proportion, is hard like stone after being coagulated and cured, and has good compression capacity but poor tension capacity. A large number of engineering practices and theoretical analyses have shown that almost all concrete components work with cracks. With the prolonging of the service time of the concrete structure, some cracks are continuously expanded under the action of use load or physical and chemical factors to form macroscopic cracks, namely concrete cracks. In order to ensure the safety and durability of concrete members, grout is generally used to repair narrow cracks.
However, most of the existing grouting materials are concrete chemical grouting materials, such as polymer mortar, polyurethane grouting materials, rubber repairing materials, epoxy resin grouting materials, etc., wherein epoxy resins have the advantages of high bonding strength, large rigidity, adjustable curing range, excellent thermal stability, good chemical corrosion resistance, and are most widely applied in organic concrete repairing. However, in the case that a water-covering layer exists on the surface of a concrete crack in a humid environment, that is, on the surface of the concrete crack, the conventional epoxy resin grouting material is difficult to effectively wet and penetrate the moist concrete base surface, so that the epoxy resin grouting material is cured to form a film only on the surface of the water-covering layer, and is prevented from further diffusing into the interior of the concrete matrix, and the bonding capacity between the surface of the concrete crack and the epoxy resin grouting material is reduced. Therefore, when repairing cracks, the use of the existing grouting material is easy to cause repair failure.
In summary, there is a need for an epoxy resin grouting material for concrete cracks in a humid environment and a preparation method thereof, which are used for solving the problem that the existing grouting material cannot effectively repair the surface of the concrete cracks with a water covering layer.
Disclosure of Invention
The first purpose of the invention is to provide an epoxy resin grouting material, which has the following specific technical scheme:
an epoxy resin grouting material comprises the following raw material components in parts by mass: 100 parts of carboxyl-terminated modified epoxy resin, 20-40 parts of curing agent, 5-10 parts of toughening agent, 2-3 parts of coupling agent, 2-5 parts of thixotropic agent, 5-10 parts of water-absorbing filler, 15-20 parts of hydrophilic diluent and 10-15 parts of aliphatic reactive diluent;
the carboxyl-terminated modified epoxy resin is dicarboxylic acid modified anionic hydrophilic epoxy resin, and the epoxy value of the epoxy resin is 0.25-0.30.
In some embodiments, the raw material components adopted by the carboxyl-terminated modified epoxy resin in modification comprise dicarboxylic acid, bisphenol A epoxy resin and a catalyst; the molar ratio of the dicarboxylic acid to the bisphenol A epoxy resin to the catalyst is (0.8-1.0) to 1;
the dicarboxylic acid comprises at least one of oxalic acid, malonic acid, succinic acid, methylmalonic acid, glutaric acid, 2-methyl-1, 4-succinic acid, dimethyl-1, 3-malonic acid, isophthalic acid, 5-hydroxyisophthalic acid, 5-methylisophthalic acid, 4-hydroxyisophthalic acid, and phthalic acid;
the catalyst comprises at least one of benzyltriethylammonium chloride, 1-butyl-3-methylimidazolium bromide, tetrabutylphosphonium bromide and triphenylphosphine.
In some embodiments, the bisphenol A type epoxy resin includes at least one of E-35, E42, E-44, E-51, and E55.
In some embodiments, the curing agent is an amine comprising at least one of ethylenediamine, diethylenetriamine, triethylenetetramine, triethanolamine, tetraethylenepentamine, dipropylenetriamine, piperidine, triethylenediamine, N-dimethylpiperazine, N-aminoethylpiperazine, isophoronediamine, m-phenylenediamine, m-xylylenediamine, 3' -dimethyl-4, 4' -diamino-dicyclohexylmethane, 4' -diaminodicyclohexylmethane, diaminodiphenylmethane, and 2-aminodiphenylsulfone.
In some embodiments, the hydrophilic diluent is at least one of tetrahydrofuran, acetone, and absolute ethanol.
In some embodiments, the toughening agent is a reactive toughening agent comprising at least one of liquid polysulfide rubber, nitrile rubber, neoprene rubber, and polyether;
the coupling agent is a silane coupling agent containing epoxy groups or amino functional groups in molecules and comprises at least one of gamma-aminopropyltriethoxysilane, gamma-aminopropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, gamma-glycidoxypropyltrimethoxysilane, N-aminoethyl-3-aminopropyltrimethoxysilane, 3-2-aminoethyl-aminopropyltrimethoxysilane, N-beta- (aminoethyl) -gamma-aminopropylmethyldimethoxysilane, N-diethyl-3-aminopropyltrimethoxysilane, 3- (2, 3-glycidoxy) propyl methyldimethoxysilane, 3- (2, 3-glycidoxy) propyl methyldiethoxysilane, gamma-glycidoxypropyltriethoxysilane and gamma-glycidoxypropyltrimethoxysilane;
the thixotropic agent comprises fumed silica, at least one of organic bentonite, hydrogenated castor oil and polyvinyl alcohol;
the water-absorbing filler comprises a first component and a second component, and the mass ratio of the first component to the second component is 4; the first component is calcium oxide; the second component comprises at least one of acrylic resin, polyvinyl alcohol resin and acrylamide;
the aliphatic reactive diluent is short-chain aliphatic polyepoxy glycidyl ether, and comprises at least one of diglycidyl ether, ethylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, 1, 4-butanediol diglycidyl ether, glycerol triglycidyl ether and trimethylolpropane triglycidyl ether.
In some embodiments, the hydrophilic diluent is of AR grade purity; the viscosity of the aliphatic reactive diluent is not more than 200mPa.s at 25 ℃.
The second purpose of the present invention is to provide a method for preparing the epoxy resin grouting material, which comprises the following steps:
the preparation method of the epoxy resin grouting material comprises the following steps:
step S1, preparing carboxyl-terminated modified epoxy resin
Specifically, bisphenol A epoxy resin with the required molar weight and catalyst aqueous solution with the required molar weight are added into a reaction kettle filled with a first organic solvent, and the mixture is stirred and reacted for 2 to 3 hours at a first heating temperature;
dissolving dicarboxylic acid with the required molar weight in a second organic solvent with the same volume, uniformly mixing, adding into the reaction kettle, and stirring and reacting at a second heating temperature for 0.5-1.5h to obtain a prefabricated product;
cooling the prefabricated object to room temperature, standing and layering the prefabricated object by using a third organic solvent to obtain a semi-finished product, and drying the semi-finished product in vacuum until the weight is constant to obtain carboxyl-terminated modified epoxy resin;
step S2, preparing the premix
Uniformly stirring and mixing the toughening agent, the coupling agent, the thixotropic agent, the water-absorbing filler, the hydrophilic diluent and the aliphatic reactive diluent in required parts by mass with the carboxyl-terminated modified epoxy resin prepared in the step S1 to prepare a premix, and sealing and storing the premix;
step S3, preparing epoxy resin grouting material
And uniformly stirring and mixing the premix and the curing agent in required parts by mass to obtain the epoxy resin grouting material.
In some embodiments, the first organic solvent and the third organic solvent are both toluene; the second organic solvent is isopropanol.
In some embodiments, the first heating temperature is from 65 ℃ to 75 ℃; the second heating temperature is 65-75 ℃; the temperature of the vacuum drying is 40-50 ℃.
The technical scheme of the invention at least has the following beneficial effects:
(1) According to the epoxy resin grouting material, carboxyl is blocked and modified, strong hydrophilic group carboxyl and hydroxyl generated in modification are introduced into a modified epoxy resin molecular chain, the affinity of the epoxy grouting material to water molecules is improved, so that the hydrophilic group of the modified epoxy molecule extends into a water-covering layer of a crack interface of a cement matrix, and the defect that the existing grouting material is not compatible with the water-covering layer is overcome;
the use of the hydrophilic diluent further improves the hydrophilicity of the epoxy resin grouting material, excessive hydrophilic diluent molecules can be selectively transferred to the wet surface of a cement matrix to displace water molecules, and the crack interface state of the matrix to be repaired is improved, so that good wetting capacity is formed on a water-covering interface;
the water-absorbing filler can absorb a large amount of water molecules in the water covering layer to form gel and keep the water molecules from flowing out under certain pressure. When the epoxy resin grouting material is in contact with a concrete crack interface and forms a blending state with an interface water-covering layer, under the hydrophilic action of the carboxyl-terminated modified epoxy resin and the hydrophilic diluent, water in the water-covering layer is rapidly contacted with the water-absorbent filler and absorbed to enable the interface to be in a dry state, and meanwhile, the pressure generated by water absorption expansion of the water-absorbent filler can effectively enlarge the permeation radius of the epoxy resin grouting material, so that the volume shrinkage rate of the cured epoxy resin grouting material is reduced while the mechanical condensation effect of the epoxy resin grouting material and a concrete matrix is enhanced. Water molecules finally exist in the epoxy resin grouting material curing system in the form of bound water, and the problem that the durability of the repairing system is insufficient due to the defect left by water evaporation after the existing grouting material is cured is solved.
(2) When the epoxy resin grouting material prepared by the invention is used for repairing concrete cracks in a humid environment, the surface structure of a water covering layer at the concrete crack interface can be effectively changed, the wettability of the epoxy resin grouting material on a water covering concrete matrix is improved, and the defect that the existing grouting material is not compatible with water is overcome. The water-absorbing filler is introduced into the epoxy resin grouting material repairing system, so that the influence of water evaporation on the strength and durability of the repairing system is eliminated. The invention can realize good grouting and bonding effect on a concrete crack interface in a humid environment, and has the characteristics of low viscosity, high strength, high toughness, high bonding force, wear resistance and corrosion resistance.
Detailed Description
The technical solutions in the present invention will be described clearly and completely with reference to the following embodiments of the present invention, and it should be understood that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments that can be derived by one of ordinary skill in the art from the embodiments given herein are intended to be within the scope of the present invention.
Example 1:
an epoxy resin grouting material comprises the following raw material components in parts by mass: 100 parts of carboxyl-terminated modified epoxy resin, 20 parts of curing agent (specifically triethylene diamine), 5 parts of toughening agent (specifically liquid nitrile rubber), 2 parts of coupling agent (specifically gamma-aminopropyltriethoxysilane), 2.5 parts of thixotropic agent (specifically fumed silica), 5 parts of water-absorbing filler (specifically calcium oxide 4 parts, acrylic acid water-absorbing resin 1 part), 20 parts of hydrophilic diluent (tetrahydrofuran, the purity is AR level) and 15 parts of aliphatic active diluent (specifically 1, 4-butanediol diglycidyl ether, the viscosity of which is 15-20mPa.s at 25 ℃) are added;
the carboxyl-terminated modified epoxy resin is dicarboxylic acid modified anionic hydrophilic epoxy resin, and the epoxy value of the epoxy resin is 0.29.
The raw material components adopted by the carboxyl-terminated modified epoxy resin during modification comprise dicarboxylic acid (specifically oxalic acid), bisphenol A type epoxy resin (specifically type E-51, purchased from Shandong Youso chemical technology Co., ltd.) and a catalyst (specifically benzyltriethylammonium chloride); the molar ratio of the dicarboxylic acid to the bisphenol A epoxy resin to the catalyst is 1;
the preparation method of the epoxy resin grouting material comprises the following steps:
step S1, preparing carboxyl-terminated modified epoxy resin
Specifically, a required molar amount of bisphenol A epoxy resin and a required molar amount of catalyst aqueous solution are added into a reaction kettle filled with a first organic solvent (specifically toluene), and the mixture is stirred and reacted for 2.5 hours at a first heating temperature (specifically 70 ℃);
dissolving dicarboxylic acid with the required molar weight in a second organic solvent (specifically isopropanol) with the same volume, uniformly mixing, adding the mixture into the reaction kettle through a dropping funnel, and stirring and reacting for 1h at a second heating temperature (specifically 70 ℃) to obtain a prefabricated product;
cooling the prefabricated object to room temperature, adding the prefabricated object into a separating funnel, adding a third organic solvent (specifically toluene), standing for layering, taking an upper layer solution, washing with water to obtain a semi-finished product, and carrying out vacuum drying (specifically drying at 50 ℃) on the semi-finished product until the weight is constant to obtain the carboxyl-terminated modified epoxy resin;
step S2, preparing the premix
Uniformly stirring and mixing the toughening agent, the coupling agent, the thixotropic agent, the water-absorbing filler, the hydrophilic diluent and the aliphatic reactive diluent in required parts by mass with the carboxyl-terminated modified epoxy resin prepared in the step S1 to prepare a premix, and sealing and storing the premix;
step S3, preparing epoxy resin grouting material
And uniformly stirring and mixing the premix and the required mass part of curing agent to obtain the epoxy resin grouting material.
Example 2:
different from the embodiment 1, the epoxy resin grouting material comprises the following raw material components in parts by mass: 100 parts of carboxyl-terminated modified epoxy resin, 40 parts of curing agent (specifically 30 parts of ethylenediamine and 10 parts of triethanolamine), 10 parts of toughening agent (specifically liquid polyether), 2 parts of thixotropic agent (specifically fumed silica), 10 parts of water-absorbing filler (specifically 8 parts of calcium oxide and 2 parts of acrylic resin), 15 parts of hydrophilic diluent (specifically acetone and with the purity of AR level) and 10 parts of aliphatic reactive diluent (specifically ethylene glycol diglycidyl ether with the viscosity of 25-45mPa.s at 25 ℃);
the epoxy value of the carboxyl-terminated modified epoxy resin is 0.26. The carboxyl-terminated modified epoxy resin is bisphenol A epoxy resin (specifically, the type is E-44, and the bisphenol A epoxy resin is purchased from Shandong Yousio chemical science and technology Co., ltd.) in raw material components.
Example 3:
different from the embodiment 1, the epoxy resin grouting material comprises the following raw material components in parts by mass: 100 parts of carboxyl-terminated modified epoxy resin, 30 parts of a curing agent (specifically diethylenetriamine), 6 parts of a toughening agent (specifically liquid polyether), 3 parts of a coupling agent (specifically 3-glycidyl ether oxypropyltriethoxysilane), 5 parts of a thixotropic agent (specifically organobentonite), 6 parts of a water-absorbing filler (specifically 4 parts of calcium oxide and 2 parts of acrylic resin), 17 parts of a hydrophilic diluent (specifically absolute ethyl alcohol and with the purity of AR level) and 12 parts of an aliphatic reactive diluent (specifically trimethylolpropane triglycidyl ether with the viscosity of 90-120mPa.s at 25 ℃);
the epoxy value of the carboxyl-terminated modified epoxy resin is 0.25. The carboxyl-terminated modified epoxy resin is bisphenol A epoxy resin (specifically, the type is E-51, and the bisphenol A epoxy resin is purchased from Shandong Yousio chemical science and technology Co., ltd.) in raw material components.
Comparative example 1:
unlike example 1, the carboxyl-terminated modified epoxy resin was a bisphenol a type epoxy resin, i.e., no modification treatment was performed.
Comparative example 2:
the difference from the example 1 is that the mass of the carboxyl end capping modified epoxy resin is 120 parts.
Comparative example 3:
the difference from the example 1 is that the mass of the carboxyl end capping modified epoxy resin is 80 parts.
Comparative example 4:
in contrast to example 1, the catalyst was tetrabutylammonium bromide.
Comparative example 5:
unlike example 1, the bisphenol a type epoxy resin was type E20.
Comparative example 6:
in contrast to example 1, acetic acid was used instead of the dicarboxylic acid.
Comparative example 7:
unlike example 1, the water-absorbent filler was 12 parts by mass.
Comparative example 8:
unlike example 1, the water-absorbent filler was 3 parts by mass.
Comparative example 9:
unlike example 1, the hydrophilic diluent was 25 parts by mass.
Comparative example 10:
unlike example 1, the mass of the hydrophilic diluent was 10 parts.
The epoxy resin grouting materials prepared in examples 1-3 and comparative examples 1-10 are used for carrying out a bonding tensile strength test and a bonding rupture strength test after repairing and bonding a fractured cement test piece, and the specific processes are as follows:
1) The cement test piece applied in the bonding tensile strength test is a tensile test piece, the tensile test piece adopts an 8-shaped cement test piece (two separated o-shaped structures are adopted, and the two o-shaped structures are bonded into the 8-shaped structure when repairing and bonding) suggested by the specification GB/T16777-2008, and the bonding tensile strength test is carried out after curing for 28 days under the standard curing condition.
Specifically, 156 tensile test pieces are randomly selected and evenly divided into 13 groups (each group comprises 12 tensile test pieces) of tensile test pieces which are respectively marked as a 1 st group, a 2 nd group, a 3 rd group, a. 6 tensile test pieces are taken from each group of 12 tensile test pieces and used for a dry bonding tensile strength experiment, and 6 tensile test pieces are used for a wet bonding tensile strength experiment. In a dry bonding tensile strength experiment, each tensile test piece needs to be air-dried at normal temperature for 4 days for repairing and bonding; in the wet bonding tensile strength test, each tensile test piece needs to be soaked (specifically, after being soaked in water for 4 days, wherein the water temperature is 18-22 ℃), the tensile test piece is taken out to wipe off the surface clear water of the cement test piece, and the bonding is repaired. In repairing the bond, equal mass (specifically m) is used 0 ) The epoxy resin grouting material prepared in the embodiment 1 is used for repairing and bonding each tensile test piece in the group 1 tensile test piece into an 8-shaped structure; using equal mass (in particular m) 0 ) The epoxy resin grouting material prepared in the embodiment 2 is used for repairing and bonding each tensile test piece in the 2 nd group of tensile test pieces into an 8-shaped structure; using equal mass (in particular m) 0 ) The epoxy resin grouting material prepared in the embodiment 3 is used for repairing and bonding each tensile test piece in the 3 rd group of tensile test pieces into an 8-shaped structure; using equal mass (in particular m) 0 ) Epoxy resin grouting material prepared by comparative example 1 to tensile test piece of group 4Repairing and bonding each tensile test piece into an 8-shaped structure; the electric power supply unit is connected with the power supply unit; using equal mass (in particular m) 0 ) The epoxy resin grouting material prepared in comparative example 10 was repaired and bonded to each tensile specimen in the 13 th group of tensile specimens in a structure of "8".
And standing the repaired and bonded tensile test pieces for 24 hours at normal temperature, and carrying out a bonding tensile strength experiment at a loading rate of 2 mm/min. The dry and wet bond tensile strength results of each group are the average value of the data of 6 tensile test pieces, and the specific results are shown in table 1.
2) The cement test piece applied in the bonding flexural strength test is a flexural test piece, the dimensions of the flexural test piece are 40mm in length, 40mm in width and 160mm in height, and after curing for 28 days under standard curing conditions, the cement test piece is cut from the middle point of the long edge of the cement test piece to perform the bonding flexural strength test.
Specifically, 156 anti-bending test pieces are randomly selected and evenly divided into 13 groups (each group comprises 12 anti-bending test pieces) of anti-bending test pieces which are respectively marked as a 1 st group, a 2 nd group, a 3 rd group, an. 6 anti-bending test pieces in each group of 12 anti-bending test pieces are used for a dry bonding anti-bending strength experiment, and 6 anti-bending test pieces are used for a wet bonding anti-bending strength experiment. In a dry bonding flexural strength test, each flexural test piece needs to be repaired and bonded after being air-dried for 4 days at normal temperature; in the wet adhesion flexural strength test, each flexural test piece needs to be soaked (specifically, soaked in water for 4 days, wherein the water temperature is 18-22 ℃), taken out and wiped to remove the surface clear water of the flexural test piece, and then the surface of the flexural test piece is repaired and adhered. In repairing the bond, equal mass (specifically m) is used 0 ) The epoxy resin grouting material prepared in the embodiment 1 is used for repairing and bonding each anti-bending test piece in the group 1 anti-bending test pieces into an integral structure; using equal masses (in particular m) 0 ) The epoxy resin grouting material prepared in the embodiment 2 is used for repairing and bonding each anti-bending test piece in the group 2 of anti-bending test pieces into an integral structure; using equal mass (in particular m) 0 ) The epoxy resin grouting material prepared in the embodiment 3 is used for repairing and bonding each anti-bending test piece in the 3 rd group of anti-bending test pieces into an integral structure; using equal masses (in particular m) 0 ) The epoxy resin grouting material prepared in comparative example 1 was applied to each of the bending-resistant test pieces of group 4Repairing and bonding the folded test piece into an integral structure; a cut-out; using equal mass (in particular m) 0 ) The epoxy resin grouting material prepared in comparative example 10 was repaired and bonded to each of the bending resistant test pieces in the 13 th group of bending resistant test pieces to form an integral structure.
And standing the repaired and bonded anti-bending test pieces for 24 hours at normal temperature, and carrying out a bonding anti-bending strength experiment at a loading speed of 50N/s. The results of the dry and wet bond flexural strength of each group are the average of the data of 6 flexural test pieces, and the specific results are shown in table 1.
TABLE 1
Figure BDA0003632066070000091
As can be seen from the data in table 1,
1) Compared with comparative example 1 and comparative examples 4-6, the carboxyl-terminated modified epoxy resin in examples 1-3 and the appropriate modification components adopted by the invention can ensure that the prepared epoxy resin grouting material has better bonding rupture strength and bonding tensile strength.
2) Compared with comparative examples 2-3 and 7-10, the carboxyl-terminated modified epoxy resin, the hydrophilic diluent and the water-absorbent filler which are used in proper amounts in examples 1-3 can ensure that the prepared epoxy resin grouting material has better bonding rupture strength and bonding tensile strength.
The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention, and various modifications and changes may be made by those skilled in the art. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.

Claims (10)

1. The epoxy resin grouting material is characterized by comprising the following raw material components in parts by mass: 100 parts of carboxyl-terminated modified epoxy resin, 20-40 parts of curing agent, 5-10 parts of toughening agent, 2-3 parts of coupling agent, 2-5 parts of thixotropic agent, 5-10 parts of water-absorbing filler, 15-20 parts of hydrophilic diluent and 10-15 parts of aliphatic reactive diluent;
the hydrophilic diluent is at least one of tetrahydrofuran, acetone and absolute ethyl alcohol;
the water-absorbing filler comprises a first component and a second component, and the mass ratio of the first component to the second component is 4; the first component is calcium oxide; the second component comprises at least one of acrylic resin, polyvinyl alcohol resin and acrylamide;
the carboxyl-terminated modified epoxy resin is dicarboxylic acid modified anionic hydrophilic epoxy resin, and the epoxy value of the epoxy resin is 0.25-0.30;
the raw material components adopted by the carboxyl-terminated modified epoxy resin during modification comprise dicarboxylic acid, bisphenol A epoxy resin and a catalyst; the molar ratio of the dicarboxylic acid to the bisphenol A epoxy resin to the catalyst is (0.8-1.0) 1:0.05; the catalyst is benzyltriethylammonium chloride.
2. The epoxy resin grouting material of claim 1, wherein the dicarboxylic acid comprises at least one of oxalic acid, malonic acid, succinic acid, methylmalonic acid, glutaric acid, 2-methyl-1, 4-succinic acid, dimethyl-1, 3-malonic acid, isophthalic acid, 5-hydroxyisophthalic acid, 5-methylisophthalic acid, 4-hydroxyisophthalic acid, and phthalic acid.
3. The epoxy resin grouting material of claim 2, wherein the bisphenol a type epoxy resin includes at least one of E-35, E42, E-44, E-51, and E55.
4. The epoxy resin grouting material of claim 2, wherein the curing agent is an amine including at least one of ethylenediamine, diethylenetriamine, triethylenetetramine, triethanolamine, tetraethylenepentamine, dipropylenetriamine, piperidine, triethylenediamine, N-dimethylpiperazine, N-aminoethylpiperazine, isophoronediamine, m-phenylenediamine, m-xylylenediamine, 3' -dimethyl-4, 4' -diamino-dicyclohexylmethane, 4' -diaminodicyclohexylmethane, diaminodiphenylmethane, and 2-aminodiphenylsulfone.
5. The epoxy resin grouting material of claim 2, wherein the toughening agent is an active toughening agent comprising at least one of liquid polysulfide rubber, nitrile rubber, neoprene, and polyether;
the coupling agent is a silane coupling agent containing an epoxy group or an amino functional group in a molecule, and comprises at least one of gamma-aminopropyltriethoxysilane, gamma-aminopropyltrimethoxysilane, 3-glycidyloxypropyltriethoxysilane, gamma-glycidyloxypropyltrimethoxysilane, N-aminoethyl-3-aminopropyltrimethoxysilane, 3-2-aminoethyl-aminopropyltrimethoxysilane, N-beta- (aminoethyl) -gamma-aminopropylmethyldimethoxysilane, N-diethyl-3-aminopropyltrimethoxysilane, 3- (2, 3-glycidoxy) propylmethyldimethoxysilane, 3- (2, 3-glycidoxy) propylmethyldiethoxysilane, gamma-glycidyloxypropyltriethoxysilane and gamma-glycidyloxypropyltrimethoxysilane;
the thixotropic agent comprises fumed silica, at least one of organic bentonite, hydrogenated castor oil and polyvinyl alcohol;
the aliphatic reactive diluent is short-chain aliphatic polyepoxy glycidyl ether which comprises at least one of diglycidyl ether, glycerol triglycidyl ether and trimethylolpropane triglycidyl ether.
6. The epoxy resin grouting material according to claim 5, wherein the diglycidyl ether includes at least one of ethylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, and 1, 4-butanediol diglycidyl ether.
7. The epoxy resin grouting material according to claim 6, wherein the purity of the hydrophilic diluent is AR grade; the viscosity of the aliphatic reactive diluent is not more than 200mPa.s at 25 ℃.
8. A method for preparing an epoxy resin grouting material according to any one of claims 2 to 7, comprising the steps of:
step S1, preparing carboxyl-terminated modified epoxy resin
Specifically, bisphenol A epoxy resin with the required molar quantity and catalyst aqueous solution with the required molar quantity are added into a reaction kettle filled with a first organic solvent, and the mixture is stirred and reacted for 2 to 3 hours at a first heating temperature;
dissolving dicarboxylic acid with the required molar weight in a second organic solvent with the same volume, uniformly mixing, adding into the reaction kettle, and stirring and reacting at a second heating temperature for 0.5-1.5h to prepare a prefabricated product;
cooling the prefabricated object to room temperature, standing and layering the prefabricated object by using a third organic solvent to obtain a semi-finished product, and drying the semi-finished product in vacuum until the weight is constant to obtain carboxyl-terminated modified epoxy resin;
step S2, preparing the premix
Uniformly stirring and mixing the toughening agent, the coupling agent, the thixotropic agent, the water-absorbing filler, the hydrophilic diluent and the aliphatic reactive diluent in required parts by mass with the carboxyl-terminated modified epoxy resin prepared in the step S1 to prepare a premix, and sealing and storing the premix;
step S3, preparing epoxy resin grouting material
And uniformly stirring and mixing the premix and the curing agent in required parts by mass to obtain the epoxy resin grouting material.
9. The method according to claim 8, wherein the first organic solvent and the third organic solvent are each toluene; the second organic solvent is isopropanol.
10. The method of claim 9, wherein the first heating temperature is 65 ℃ to 75 ℃; the second heating temperature is 65-75 ℃; the temperature of the vacuum drying is 40-50 ℃.
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