KR20190008606A - Expansible organic-inorganic hybrid grouting solution and method for construction using the same - Google Patents

Abstract

Provided, in the present invention, is a 2-liquid type expandable organic-inorganic composite grouting chemical solution composition comprising: (a) silica sol obtained by mixing an aluminum sulfate solution and a sulfuric acid solution with a silicate solution; (b) an aqueous solution containing at least one carboxyl group containing ethylenically unsaturated monomer metal salt, selected from a group consisting of sodium salt, potassium salt, lithium salt, magnesium salt and calcium salt of acrylic acid, methacrylic acid, 3,3-dimethyl acrylic acid, crotonic acid, maleic acid, fumaric acid, itaconic acid or mesaconic acid, an acrylamide derivative or a mixture thereof, and a crosslinking agent; (c) a first solution containing a reducing catalyst; (d) a hardener; and (e) a second solution containing an oxidizing catalyst.

Description

TECHNICAL FIELD [0001] The present invention relates to an expandable organic-inorganic hybrid grouting solution and a construction method using the same,

The present invention relates to an expandable organic-inorganic composite grouting chemical liquid composition and a method of applying the same, and more particularly, to an expandable organic-inorganic composite grouting chemical liquid composition which imparts swelling property by forming a water swellable acrylic polymer during curing of a grouting chemical injection material And a method for performing grouting by using the same.

In general, in order to prevent the inflow or outflow of groundwater in civil engineering and construction work, a construction method is performed in which a chemical solution is injected into the ground for the purpose of indexing joints and cracks in the underground groundwater, concrete structures and the like. Conventionally, the chemical solution used in the ground injection is largely composed of polymeric organic substances such as phenol resin, epoxy system, acrylamide system and urethane system, and cement milk and sodium silicate inorganic substance.

However, when the grouting is performed by injecting a chemical solution mainly composed of the polymeric organic material such as the epoxy or urethane system into the soft ground, excellent exponential effect is obtained by initial foaming or hardening, but after a long time, The exponential effect is lowered due to shrinkage or the like, which limits the durability (Patent Document 1).

On the other hand, the sodium silicate chemical solution, which is the most commonly used inorganic substance, has an advantage in that the cost can be reduced because the cost is lower than that of the polymeric organic chemical solution. However, as time elapses after the injection, The leaching of alkali components caused the loss of durability such as loss or disappearance of the injected material, or environmental problems such as contamination of groundwater. Therefore, in the industry, there has been a steady demand for the modification of the sodium silicate chemical solution. The inventors of the present invention have developed a chemical solution of the colloidal sol which is modified with the sodium silicate chemical solution so as to include the active reactant of the aqueous solution of the alkaline earth metal salt. The present invention has been made to solve the above-mentioned problems, and it is an object of the present invention to provide a method for producing a grout injection material which comprises silica colloid as a main component.

Therefore, the inventors of the present invention have conducted extensive research for developing a chemical solution for grouting construction. As a result, they have found that a silica sol solution obtained by treating silicic acid with sulfuric acid constitutes a first solution with components including an acrylic monomer and a crosslinking agent, When the second solution is composed of a component containing a curing agent to prepare an organic-inorganic hybrid chemical liquid and then subjected to grouting, the compressive strength of the gel is greatly improved and the elasticity of the acrylic polymer is increased due to the swelling property of the acrylic polymer. And the durability is increased due to no leaching of the alkali components even after a long time after the grouting is completed. The present invention has been accomplished based on this finding.

Patent Document 1: Korean Patent Laid-Open Publication No. 10-1994-0002344

Patent Document 2: Korean Patent Publication No. 10-0370880

Patent Document 3: Korean Patent Publication No. 10-0684185

SUMMARY OF THE INVENTION Accordingly, the present invention has been made keeping in mind the above problems occurring in the prior art, and it is an object of the present invention to provide an acrylic polymer composition which not only has a great improvement in compressive strength of a gel but also has elasticity and adhesiveness with the ground, Inorganic composite grouting chemical composition and a method of using the same, wherein the durability of the expandable organic-inorganic composite grouting chemical composition is improved due to no leaching of alkali components even after a long period of time after the grouting.

According to an aspect of the present invention, there is provided a method for producing a silica sol comprising the steps of: a) mixing a silicate solution with an aluminum sulfate solution and a sulfuric acid solution; b) Containing at least one carboxyl group-containing ethylenically unsaturated monomer selected from the group consisting of sodium salt, potassium salt, lithium salt, magnesium salt and calcium salt of fumaric acid, itaconic acid or mesaconic acid, or a mixture thereof and a crosslinking agent , C) a first solution containing a reducing catalyst; And d) a curing agent, and e) an oxidation catalyst. The two-pack type expandable organic-inorganic composite grouting chemical solution composition comprises:

The silicate is characterized by at least one selected from the group consisting of liquid sodium silicate, liquid potassium silicate and liquid lithium silicate.

The acrylamide derivative is at least one selected from the group consisting of acrylamide, N-methylacrylamide, N-ethyl acrylamide, N, N-dimethylacrylamide and N, N-diethylacrylamide.

The crosslinking agent is selected from the group consisting of ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, polyethylene glycol di , Trimethylolpropane tri (meth) acrylate, N, N'-methylenebisacrylamide, N, N'-ethylenebisacrylamide, N, N'-hexamethylenebisacrylamide, polyethylene glycol diglycidyl ether, Glycerin diglycidyl ether, and a mixture thereof.

 The reduction catalyst is any one selected from the group consisting of tetramethylethylenediamine, diethanolamine, triethanolamine, nitrilotris (propionamide), and dimethylaminopropionitrile.

The curing agent is any one selected from the group consisting of liquid sodium silicate, liquid sodium hydroxide, liquid sodium carbonate, liquid potassium oxide and liquid calcium hydroxide.

The oxidation catalyst is characterized by being sodium persulfate, potassium persulfate or ammonium persulfate.

Wherein the weight ratio of the first solution to the second solution is from 2: 8 to 8: 2.

Also, the present invention provides a grouting method comprising a gelling step of mixing and gelling the first solution and the second solution.

The two-pack type expandable organic-inorganic composite grouting chemical composition prepared according to the present invention not only greatly improves the compressive strength of the gel after the application but also maintains the elasticity and adhesion with the ground due to the swelling property of the acrylic polymer, Even after a long time, the alkali components are not leached and the durability is increased, so that the stable grouting can be performed.

BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a simplified process diagram from an expandable organic-inorganic composite grouting chemical composition of the present invention to a grouting application. FIG.

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, a two-pack type expandable organic-inorganic composite grouting chemical composition according to the present invention and a construction method using the same will be described in detail.

First, the present invention provides a method for preparing a silica sol comprising the steps of: a) mixing a silica sol in which a solution of aluminum sulfate and a solution of sulfuric acid is mixed in a silicate solution, b) a silica sol mixed with acrylic acid, methacrylic acid, 3,3-dimethyl acrylic acid, crotonic acid, maleic acid, fumaric acid, An aqueous solution containing a metal salt, an acrylamide derivative or mixtures thereof and a crosslinking agent of at least one carboxyl group-containing ethylenically unsaturated monomer selected from the group consisting of sodium salt, potassium salt, lithium salt, magnesium salt and calcium salt, c) ≪ / RTI > And d) a curing agent, and e) an oxidation catalyst. The two-pack type expandable organic-inorganic composite grouting chemical solution composition comprises:

The silica sol as the component a) can be obtained by mixing an aluminum sulfate solution and a sulfuric acid solution in a silicate solution, and the silicate solution is diluted with water to form a silicate solution. On the other hand, a treatment in which an aluminum sulfate solution and a sulfuric acid solution are blended A silica sol as an inorganic substance can be easily formed by mixing the silicate solution and the sulfuric acid treatment solution in a high-speed rotary reactor or the like.

At this time, as the silicate, at least one selected from the group consisting of liquid sodium silicate, liquid potassium silicate and liquid lithium silicate is preferably used, and liquid sodium silicate is more preferably used.

The two-pack type expandable oil-and-inorganic composite grouting chemical liquid composition according to the present invention ultimately mixes the first solution and the second solution to form a water-swellable acrylic polymer during curing by progressing a chain polymerization reaction and a crosslinking reaction, Inorganic composite of a gel structure in which inorganic particles of silica particles are entangled in an organic polymeric polymer chain. Therefore, when the two-pack type expandable organic-inorganic hybrid grouting chemical composition of the present invention is injected into cracks, cracks, joints or the like of a ground or a concrete structure requiring exponent or order of groundwater, it changes into a gel structure in the ground and performs a sealing function Exponent or order of the objective can be achieved.

In this case, the chain polymerization may be carried out in the presence of a catalyst such as sodium salt, potassium salt, lithium salt, magnesium salt of acrylic acid, methacrylic acid, 3,3-dimethyl acrylic acid, crotonic acid, maleic acid, fumaric acid, itaconic acid, A metal salt, an acrylamide derivative or a mixture thereof of at least one carboxyl group-containing ethylenically unsaturated monomer selected from the group consisting of a salt and a calcium salt is subjected to a radical polymerization reaction by a redox initiator combined with a reduction catalyst and an oxidation catalyst Thereby forming a polymer.

Conventionally, acrylamide-based monomers have been mainly used as polymerizable organic substances in a chemical solution for ground injection. However, because of the toxicity of the unreacted acrylamide monomers which are not polymerized, There is a limitation in the present invention. Therefore, in the present invention, in the use of the acrylamide-based monomer as the polymerizable organic substance, the problem of environmental pollution can be fundamentally solved by preventing the unreacted acrylamide derivative from remaining by controlling the polymerization reaction conditions.

The acrylamide derivative may be at least one selected from the group consisting of acrylamide, N-methyl acrylamide, N-ethyl acrylamide, N, N-dimethylacrylamide and N, N-diethylacrylamide, Acrylamide is more preferably used because it can control the swelling degree of the gel to about three times when the gel is formed.

Further, it is also possible to use 1, 2 or 3 groups selected from the group consisting of sodium salts, potassium salts, lithium salts, magnesium salts and calcium salts of acrylic acid, methacrylic acid, 3,3-dimethyl acrylic acid, crotonic acid, maleic acid, fumaric acid, itaconic acid, In order to form a water-swollen gel in which a metal salt, an acrylamide derivative, or a mixture thereof of a carboxyl group-containing ethylenically unsaturated monomer or a mixture thereof is subjected to a chain polymerization reaction, a crosslinking reaction must be carried out so that the polymer chain has a three- Should be used.

Examples of the crosslinking agent include ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, polyethylene glycol di (Meth) acrylate, N, N'-methylenebisacrylamide, N, N'-ethylenebisacrylamide or N, N'-hexamethylenebisacrylamide. At least one compound selected from the group consisting of a compound having two or more unsaturated groups or a polyepoxy compound such as polyethylene glycol diglycidyl ether and glycerin diglycidyl ether and a mixture thereof is used. Particularly, the use of polyethylene glycol di (meth) acrylate (PEGDA) is more preferable because it can control the water swelling degree and swelling strength as well as being involved in the crosslinking reaction. Further, when N, N'-methylene bisacrylamide (MBA) It is better to use it together.

The content of the cross-linking agent is preferably in the range of 0.5 to 10 mol% based on the total weight of the acrylic acid, methacrylic acid, 3,3-dimethyl acrylic acid, crotonic acid, maleic acid, fumaric acid, itaconic acid, or mesaconic acid sodium salt, potassium salt, lithium salt, Is preferably 1 to 10% by weight based on the content of the metal salt, the acrylamide derivative, or the mixture thereof of the at least one carboxyl group-containing ethylenically unsaturated monomer selected from the group consisting of If the content of the crosslinking agent is less than 1% by weight, the crosslinking degree is lowered and gelation is difficult to occur, and even if a part of the gel is partially formed due to the progress of the crosslinking reaction, the compressive strength may be very low. On the other hand, when the content of the cross-linking agent exceeds 10% by weight, the degree of crosslinking is too high, so that the compressive strength of the formed gel can be increased, but a brittle problem may occur even with a small impact.

Further, it is also possible to use 1, 2 or 3 groups selected from the group consisting of sodium salts, potassium salts, lithium salts, magnesium salts and calcium salts of acrylic acid, methacrylic acid, 3,3-dimethyl acrylic acid, crotonic acid, maleic acid, fumaric acid, itaconic acid, An initiator is required to chain-polymerize a metal salt, an acrylamide derivative, or a mixture thereof of a carboxyl group-containing ethylenically unsaturated monomer by a radical polymerization reaction mechanism. In general, an ethylenic unsaturation having a carbon- As the radical initiator for the chain polymerization of monomers, a photoinitiator, a thermal decomposition initiator or a lidox initiator may be used. In the present invention, considering the occurrence of a chain polymerization reaction in an aqueous solution, a lidox initiator, which is a combination of a reduction catalyst and an oxidation catalyst, use.

Particularly, as the c) component, a reducing catalyst is used. As the reducing catalyst, in combination with an oxidation catalyst, which is a component (e) described later, the reducing catalyst is used in combination with the above-mentioned acrylic acid, methacrylic acid, 3,3-dimethyl acrylic acid, crotonic acid, , A metal salt, an acrylamide derivative or a mixture thereof of at least one carboxyl group-containing ethylenically unsaturated monomer selected from the group consisting of sodium salt of itaconic acid or mesaconic acid, potassium salt, lithium salt, magnesium salt and calcium salt is subjected to chain polymerization It acts as a lidocisin initiator to carry out. At this time, as the reducing catalyst, an amine compound can be used, and in particular, any one selected from the group consisting of tetramethylethylenediamine, diethanolamine, triethanolamine, nitrilotris (propionamide) and dimethylaminopropionitrile is preferable And triethanolamine (TEA) is more preferably used.

In addition, the two-pack type expandable organic-inorganic composite grouting chemical solution composition of the present invention contains d) a curing agent as one component of the second solution, and the curing agent acts to cure the silica sol as one component of the first solution However, the silica sol exhibits a property of forming a neutral solid by completely gelling in a neutral region (pH 6 to 8) by a curing agent. In addition, since the silica sol is in a polymer state in which the molecular weight is increased to some extent, unlike the case where the ordinary water glass solution is cured, the mechanical properties and durability of the solidification agent are further improved when solidified by the curing agent. Therefore, alkali leaching phenomenon hardly occurs, and grouting can be carried out by an eco-friendly method which does not cause the problem of water pollution by dilution or loss by a large amount of water after curing or curing.

As the curing agent, any one selected from the group consisting of liquid sodium silicate, liquid sodium hydroxide, liquid sodium carbonate, liquid potassium oxide and liquid calcium hydroxide is preferably used.

The second solution contains, as one component, an oxidation catalyst. As the oxidation catalyst, a persulfate-based compound can be used. Among them, sodium persulfate, potassium persulfate or persulfate Ammonium persulfate is more preferably used. Wherein the content of the oxidation catalyst in the first solution and the oxidation catalyst in the second solution is such that the total amount of the combination of the reduction catalyst and the oxidation catalyst to function as a redox initiator is at least one selected from the group consisting of acrylic acid, A metal salt, an acrylamide derivative or a mixture thereof of at least one carboxyl group-containing ethylenically unsaturated monomer selected from the group consisting of sodium salt, potassium salt, lithium salt, magnesium salt and calcium salt of maleic acid, fumaric acid, itaconic acid or mesaconic acid, The amount of the crosslinking agent is preferably adjusted to 0.1 to 5% by weight based on the combined weight of the crosslinking agent, because unreacted monomers do not remain and the chain polymerization and crosslinking reactivity are improved and the gelation time is shortened.

In addition, ultimately, the above-mentioned first liquid and second liquid are mixed and reacted to form an expandable organic-inorganic hybrid hydrogel. As a result, the first liquid and the second liquid constituting the two-pack type expandable organic-inorganic hybrid grouting chemical composition of the present invention The weight ratio of the liquid to the second liquid is preferably from 2: 8 to 8: 2, because mechanical properties such as gel compressive strength can be maximized.

According to another aspect of the present invention, there is provided a grouting method comprising mixing a first solution and a second solution to form a gelling agent, wherein the grouting method can be performed according to a known method, A detailed description related to the construction method will be omitted. FIG. 1 shows a simplified process diagram from the inventive expandable organic-inorganic composite grouting chemical composition to grouting.

Specific examples and comparative examples are described below.

(Example)

90 L of liquid sodium silicate was added to 100 L of water to form a dilute solution. On the other hand, 10 L of a 7% strength aluminum sulfate solution and 10 L of a 70% strength sulfuric acid solution were added to prepare a treatment solution. The treatment solution was mixed and stirred to obtain silica sol. Further, 50 parts by weight of an aqueous solution of acrylic acid and methacrylic acid (molar ratio 1: 1) was slowly added dropwise to 1000 parts by weight of an aqueous solution of 30% by weight of sodium hydroxide and potassium hydroxide (molar ratio 1: An aqueous solution of sodium salt and potassium salt of acrylic acid and methacrylic acid monomer was obtained by an acid-base neutralization reaction. Subsequently, an aqueous solution of 20 wt% of an acrylamide monomer aqueous solution mixed with the sodium salt and potassium salt aqueous solution of acrylic acid and methacrylic acid monomer (sodium salt of acrylic acid and methacrylic acid monomer and 90 wt% of potassium salt aqueous solution: acrylamide monomer 10% by weight aqueous solution). 2% by weight of polyethylene glycol diacrylate (PEGDA) and N, N'-methylenebisacrylamide (MBA) based on the mixed aqueous solution were added to and dissolved in the mixed aqueous solution to obtain a uniform polymerizable aqueous solution. To the homogeneous polymerizable aqueous solution was added 1 wt% of triethanolamine (TEA) to the polymerizable aqueous solution, and then the silica sol was mixed to prepare a first solution. On the other hand, 35 kg of sodium silicate as a curing agent was dissolved in water to obtain 200 L of sodium silicate solution, and 1% by weight of sodium persulfate was added to the polymerizable aqueous solution as one component of the first solution to prepare a second solution, Thereby preparing a two-pack type expandable oil-and-inorganic composite grouting chemical liquid composition.

(Comparative Example 1)

The procedure of Example 1 was repeated except that the treatment solution containing the aluminum sulfate solution and the sulfuric acid solution was not used at the time of forming the silica sol as one component of the first solution.

(Comparative Example 2)

Except that the polymerizable aqueous solution and triethanolamine of the above Example were not used as one component of the first solution and sodium persulfate of the above-mentioned Example was not used as one component of the second solution.

Table 1 shows the gelation time measured immediately after the gel was formed by mixing the first solution and the second solution prepared in Examples and Comparative Examples 1 and 2 at a weight ratio of 1: 1, the gel compression strength after 1 month, Leaching phenomenon.

Example Gel time Gel Compression Strength (kgf / cm ² ) Leaching phenomenon Example 8.5 seconds 2.3 Not at all Comparative Example 1 10 minutes 0.4 Many occur Comparative Example 2 9.4 seconds 1.2 Many occur

As shown in Table 1, the gel formed from the examples of the present invention had much shorter gelation time than the gel formed from the comparative examples 1 and 2, significantly improved the gel compressive strength after one month, Is not present at all.

Therefore, the two-pack type expandable organic-inorganic hybrid grouting chemical composition prepared according to the present invention not only greatly improves the compressive strength of the gel after application but also maintains its elasticity and adhesion with the ground due to the swelling property of the acrylic polymer , The alkali components are not leached out even after a long time, and the durability is increased, so that the stable grouting can be performed.

Claims (9)

a) a silica sol mixed with an aluminum sulfate solution and a sulfuric acid solution in a silicate solution, b) a sodium salt of acrylic acid, methacrylic acid, 3,3-dimethyl acrylic acid, crotonic acid, maleic acid, fumaric acid, itaconic acid or mesaconic acid, An aqueous solution containing a metal salt, an acrylamide derivative or a mixture thereof, and a crosslinking agent of at least one carboxyl group-containing ethylenically unsaturated monomer selected from the group consisting of a salt, a lithium salt, a magnesium salt and a calcium salt, c) solution; And
d) a curing agent, and e) an oxidizing catalyst. The two-pack type expandable oil-and-inorganic composite grouting chemical solution composition according to claim 1, The two-pack type expandable organic-inorganic composite grouting chemical solution composition according to claim 1, wherein the silicate is at least one selected from the group consisting of liquid sodium silicate, liquid potassium silicate and liquid lithium silicate. The method of claim 1, wherein the acrylamide derivative is at least one selected from the group consisting of acrylamide, N-methylacrylamide, N-ethyl acrylamide, N, N-dimethylacrylamide and N, N- Wherein the two-component type expandable oil-and-inorganic composite grouting chemical solution composition is characterized by comprising: The method of claim 1, wherein the crosslinking agent is selected from the group consisting of ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, tetraethylene glycol di (Meth) acrylate, N, N'-ethylenebisacrylamide, N, N'-hexamethylenebisacrylamide, polyethylene glycol (meth) acrylate, Wherein at least one selected from the group consisting of glycerin diglycidyl ether, diglycidyl ether, glycerin diglycidyl ether, and mixtures thereof. 2. The process according to claim 1, wherein the reducing catalyst is any one selected from the group consisting of tetramethylethylenediamine, diethanolamine, triethanolamine, nitrilotris (propionamide) and dimethylaminopropionitrile. Wherein the composition of the organic - inorganic composite grouting solution is. The two-pack type expandable organic-inorganic composite grouting chemical solution composition according to claim 1, wherein the curing agent is any one selected from the group consisting of liquid sodium silicate, liquid sodium hydroxide, liquid sodium carbonate, liquid potassium oxide and liquid calcium hydroxide. The two-pack type expandable oil-inorganic hybrid grouting chemical solution composition according to claim 1, wherein the oxidation catalyst is sodium persulfate, potassium persulfate or ammonium persulfate. The two-pack type expandable organic-inorganic composite grouting chemical solution composition according to claim 1, wherein the weight ratio of the first solution to the second solution is 2: 8 to 8: 2. 9. A grouting method comprising mixing a first solution and a second solution according to any one of claims 1 to 8 for gelling.

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