KR100730796B1 - Acrylate based agent for blocking water leakage - Google Patents

Abstract

Acrylate based water blocking agent containing hydro-gel hydrate is provided to have excellent eco-friendly and physical properties such as curing time, curing strength and water blocking constant which are sufficient to be applied on concrete structures such as a tank, tunnel drainage duct, by comprising acrylate compound and oxidation-reduction polymerizing catalyst to form the hydro-gel hydrate. The water blocking agent is prepared by adding persulate compound and amine compound as oxidation-reduction polymerizing catalysts to acrylate based compound in order to form hydro-gel hydrate as the water blocking catalyst. The acrylate based compound is hydrophilic epoxy diacrylate compound including metal salts of acrylic acid, which are obtainable by adding acrylic acid and methacrylic acid to metal hydroxide solution, and amine groups as a cross-linking agent. The hydrophilic epoxy diacrylate compound is produced by Michael addition of epoxy triacrylate compound and secondary amine compound in 1:1 molar ratio.

Description

Acrylate based agent for blocking water leakage

The present invention relates to a water repellent used in the order and reinforcement of underground subsurfaces and the index of various concrete structures such as tanks, tunnels, sewer pipes, etc. The present invention relates to a water repellent which can be produced in a relatively easy and economical manner by a water repellent which can satisfy various properties such as curing time and strength and order coefficient.

The water repellents are used for the order and reinforcement of underground subsurfaces and indexes of various concrete structures such as tanks, tunnels, sewer pipes in civil engineering and construction works. Currently, water repellents such as cement, sodium silicate, urethane, and acrylic are used.

Cement system of the ordering agent is poor in permeability due to the high viscosity, hardening time is very slow, it requires a hardening time of about 1 hour is not suitable for the indexing and ordering process that requires rapidity, dilution, loss and contact hard to contact with water leakage There is this.

Inorganic water repellents such as sodium silicate are inexpensive, but they lack strength such as compressive strength, and the cured product is decomposed by water over time, so that the strength decreases and shrinks, thereby failing to exhibit continuous ordering performance.

Urethane-based fillers are most commonly used as fillers because of their excellent compressive and flexural strengths that can provide sufficient order strength. However, urethane-based water repellents are a major component of organic materials such as polyisocyanates and polyols, which may cause fire, skin irritation, and relatively high viscosity of the composition. If there is a tendency to decompose and shrink during drying, there is a problem of forming a permeable structure that does not properly prevent water penetration.

Acrylic water repellent has low viscosity of the composition, so it has excellent permeability to fine gaps and cracks in the layers, freely control of curing time, and forms impermeable hardened material to form a water-repellent hardened material and does not deteriorate chemically. It is widely used in the order and reinforcement of steel and index of various concrete structures.

The acrylic water-based agent currently used may be divided into acrylamide-based acrylamide and acrylate-based acrylic acid metal salts, and a mixture of acrylamide-acrylates.

Acrylamide-based water-soluble agent is mixed with acrylamide as a monomer and N, N'-methylenebisacrylamide as a crosslinking agent, dissolved in water to make an aqueous solution, and injected into the ground by adding a persulfate compound and an amine compound as a redox polymerization catalyst. It is a composition showing the order and exponential effect by causing a chain polymerization reaction in the ground to form a hydrous hydrogel. Acrylamide-based water repellents are considered to be the best among the water repellents because of their excellent physical properties and durability, but the toxic properties of acrylamide and N, N'-methylene bisacrylamide, which are the main components, are very strong. Because of this, its use is limited.

The acrylate-based water-based agent is composed of monohydric compounds such as sodium and potassium of acrylic acid and methacrylic acid, and divalent metal salts such as calcium and magnesium, and a hydrophilic polyfunctional compound such as polyethylene glycol diacrylate as a crosslinking agent. Sulfate and amine compounds are added as redox polymerization catalysts and injected into the ground to cause chain polymerization in the ground to form hydrous hydrogels. The acrylate-based water-repellent agent has a relatively low harmfulness, but there is a problem in application due to insufficient compression and flexural strength of the resulting hydrogel.

The acrylamide-based and acrylate-based mixed systems are suited to solve the problems of both by appropriately mixing the acrylamide-based and acrylate-based components. However, the toxicity and physical property problems are still present.

Accordingly, an object of the present invention is to solve the above-mentioned problems, and to provide an acrylate-based water repellent which can be economically manufactured with excellent physical properties, eco-friendly and easy manufacturing process.

In order to achieve the above object, the present invention is characterized by introducing a hydrophilic epoxy diacrylate containing an amine group as a crosslinking agent of the metal acrylate salt in the acrylate composition.

The present invention to achieve the above technical problem,

Persulfate and amine compounds are added to the acrylate compound as a redox polymerization catalyst to form hydrous hydrogels, and the index of various concrete structures such as tanks, tunnels and sewer pipes in civil engineering and building construction In the acrylate-based water used in the

The acrylate compound is an acrylic acid salt prepared by adding acrylic acid and methacrylic acid to a metal hydroxide aqueous solution and a hydrophilic epoxy diacrylate compound containing an amine group as a crosslinking agent.

In the acrylate-based ordering agent according to the present invention as described above, the hydrophilic epoxy diacrylate compound containing the amine group is subjected to a 1: 1 molar ratio Michael Addition of the epoxy triacrylate compound and the secondary amine compound. There is a feature that can be easily manufactured by.

In the acrylate-based water repellent agent according to the present invention as described above, the epoxy triacrylate compound that can be used for the preparation of the hydrophilic epoxy diacrylate compound containing the amine group is triacrylate of trimethylolpropane triglycidyl ether, glycerol Triacrylate of triglycidyl ether, sorbitol triglycidyl ether triacrylate, etc. are preferable, and as a secondary amine compound, diethylamine, dipropylamine, dibutylamine, methylethanolamine, ethylethanolamine, diethanol Amines, dicyclonuclear amines, and the like, and hydrophilic compounds can be prepared by selecting appropriate epoxytriacrylate compounds and secondary amines.

The hydrophilic epoxy diacrylate compound including the amine group used in the acrylate-based water-based according to the present invention as described above can form a robust hydrogel by the epoxy structure and the added amine group gives a hydrophilicity and at the same time redox It is a very innovative compound that can act as a reducing catalyst in the polymerization reaction to compensate for the weakness of the physical properties of the existing acrylate-based filler to provide an excellent acrylate-based filler.

Incidentally, the hydrophilic epoxy diacrylate compound including the amine group is expected to contribute to the environment in part by fixing the acid generated by decomposition of the persulfate used as the redox catalyst to the hydrogel by quaternization.

Hereinafter, the present invention will be described in more detail.

The acrylic acid metal salts used as the main component of the acrylate-based water-ordering agent of the present invention include acrylic acid and a single or mixed aqueous solution of monovalent metal hydroxides such as lithium hydroxide, potassium hydroxide and sodium hydroxide, and divalent metal hydroxides such as magnesium hydroxide and calcium hydroxide. A single or a mixture of methacrylic acid can be added dropwise, neutralized and simply synthesized.

The hydrophilic epoxy diacrylate compound including the amine group used in the present invention can be synthesized simply by dropping and reacting the single or mixed liquid of the secondary amine at 40 ° C. in a molar ratio of 1: 1 to the single or mixed liquid of the epoxy triacrylate. .

As the oxidation polymerization catalyst used in the present invention, amines such as triethylamine, triethanolamine, and diethanolamine may be used as a reducing catalyst, either singly or in combination, and persulfates such as ammonium persulfate and sodium persulfate as oxidation catalysts. Use a single or mixed.

The water-repellent agent of this invention is manufactured and used in two-component form. The first liquid is prepared by adding a hydrophilic epoxy diacrylate compound containing the amine group and the amines as the reducing catalyst to the aqueous metal salt of acrylic acid, and the second liquid is prepared by dissolving the persulfate, the oxidation catalyst, in water. . Separately, the amines, which are the reducing catalysts, may be packaged in a separate container and added to the first liquid according to external variables such as construction temperature to be used as a reaction rate regulator.

The reaction rate of the hydrogel formation of the water repellent agent according to the present invention is arbitrarily determined by the concentration of the first liquid, the concentration of the second liquid, the concentration of the amines as the reducing catalyst, the addition amount of the hydrophilic epoxy diacrylate compound including the amine group, and the construction temperature. It can be controlled at the rate of, the reaction rate is increased in proportion to the increase in the concentration and content and the construction temperature and is slowed in proportion to the drop in the concentration and content and the construction temperature.

The reaction rate of hydrogel formation of the water repellent agent according to the present invention should be adjusted to an appropriate time by appropriately combining the above factors. If the reaction rate of hydrogel formation is too fast, it will harden before the water-repellent agent penetrates to the ground to a sufficient distance. If the reaction rate of formation of hydrogel is too slow, it will be diluted by groundwater to form hydrogel for order and index. There is no possibility.

The hardness of the hydrogel formed by the water repellent agent according to the present invention can be adjusted to an arbitrary hardness by the concentration of the first liquid, the concentration of the second liquid and the amount of the hydrophilic epoxy diacrylate compound including an amine group. The hardness of the hydrogel formed in proportion to the concentration of the first liquid, the concentration of the second liquid and the addition amount of the hydrophilic epoxy diacrylate compound including an amine group is increased, and the hardness of the first liquid and the concentration of the second liquid The hardness of the hydrogel formed in proportion to the decrease in the addition amount of the hydrophilic epoxydiacrylate compound including the amine group is lowered. In general, the hardness of the hydrogel formed by the divalent metal salt is higher than the hardness of the hydrogel by the monovalent metal salt and the hardness of the hydrogel formed by acrylic acid is higher than the hardness of the hydrogel by methacrylic acid.

The hardness of the hydrogel formed by the water repellent agent according to the present invention should be adjusted to an appropriate hardness by appropriately adjusting the above factors. When the strength of the hydrogel is too high, it tends to be broken easily, and when the strength of the hydrogel is too low, it becomes a grass-like form and cannot exhibit order and index performance.

The concentration of the first liquid for controlling the reaction rate of the hydrogel formation and the hardness of the formed hydrogel according to the order and index is suitably in the range of 5% by weight to 50% by weight in aqueous solution. When the concentration of the first liquid is less than 5% by weight in aqueous solution, the reaction rate of hydrogel formation and the hardness of the formed hydrogel are too low. When the concentration of the first solution is 50% by weight or more, the reaction rate of hydrogel formation and the hardness of the formed hydrogel are excessively low. It is not desirable to be high.

The amount of the hydrophilic epoxy diacrylate compound including the amine group for controlling the hardness of the hydrogel formed appropriately in the order and index is in the range of 5% by weight to 20% by weight of the total amount of the metal acrylates. When the amount of the hydrophilic epoxy diacrylate compound including the amine group is less than 5% by weight of the total amount of the metal acrylate salt, the hardness of the formed hydrogel becomes too low to exhibit order and index performance, and the hydrogel is more than 20% by weight. It is not preferable that the hardness of the hydrogel is easily broken due to excessively high hardness.

The addition amount of the reduction reaction catalyst and the oxidation reaction catalyst for controlling the formation rate of the hydrogel according to the order and the index is the total amount of the metal acrylate metal salt of the first liquid and the addition amount of the hydrophilic epoxy diacrylate compound including the amine group. A range of 1% to 10% by weight of the total amount of the combined polymerizable compounds is appropriate. When the addition amount of the reduction reaction catalyst and the oxidation reaction catalyst is less than 1% by weight of the total amount of the polymerizable compound of the first liquid, the reaction rate of hydrogel formation is too low, making it difficult to form a hydrogel. It is not preferable that the reaction rate of formation becomes too fast and the curing agent hardens before penetrating the ground to a sufficient distance.

It is also possible to add and use additive materials, such as cement, bentonite, and diatomaceous earth, for the increase and reinforcement to the water repellent agent by this invention as needed.

Water-repellent agent according to the present invention is injected into the ground through an injection hole perforated by an appropriate injection equipment such as a two-component injection pump, and the first liquid and the second liquid of the injected water-repellent agent is mixed to produce a hydrous hydro by a redox polymerization reaction. The gel is formed and fixed to the ground to exhibit order and index performance.

Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples, and the present invention can be variously applied within the above development scope and is not limited to the following Examples.

(Assessment Methods)

-Mixing viscosity: KSF 4923 epoxy resin for repairing concrete structures

-Curing time: The time elapsed after mixing the first liquid and the second liquid at one time until the fluidity disappeared by the formation of hydrogel

-Elongation rate: KSF 3211 roof coating waterproofing material

-Tensile strength, tensile shear bond strength: KSF 4923 epoxy resin for repairing concrete structures

Permeability coefficient: KSF 2322 soil permeability test method

Example 1

Acrylic acid was added dropwise to the aqueous sodium hydroxide solution over 1 hour under cooling, followed by stirring to neutralize to form a 30% aqueous sodium acrylate solution. Separately, a hydrophilic epoxy diacrylate compound containing an amine group was maintained by dropping a diethanolamine over 1 hour while stirring at 1 mol ratio of trimethylolpropanetriglycidyl ether at 40 DEG C while stirring at 1 mol ratio. Was synthesized.

3 parts by weight of a hydrophilic epoxy diacrylate compound containing the amine group and 1.5 parts by weight of triethanolamine were added to 100 parts by weight of the aqueous sodium acrylate solution to prepare a first liquid.

2 parts by weight of sodium persulfate was dissolved in 98 parts by weight of water to prepare a second liquid.

After mixing the first liquid and the second liquid at a time, the curing time was measured and the physical properties of the formed hydrogel were measured.

Example 2

The experiment was conducted in the same manner as in Example 1 except that acrylic acid was added dropwise to the magnesium hydroxide aqueous solution over cooling for 1 hour, stirred, and neutralized to form a 30% magnesium acrylate aqueous solution.

Example 3

The experiment was conducted in the same manner as in Example 1 except that methacrylic acid was added dropwise to the aqueous magnesium hydroxide solution over 1 hour under cooling, stirred, and neutralized to form a 30% aqueous sodium methacrylate solution.

(Comparative Example 1)

The experiment was conducted in the same manner as in Example 1, except that 1 part by weight of a hydrophilic epoxydiacrylate compound including an amine group was added.

(Comparative Example 2)

The experiment was carried out in the same manner as in Example 1 except that 3 parts by weight of polyethylene glycol diacrylate was added instead of 3 parts by weight of the hydrophilic epoxy diacrylate compound including an amine group.

(Comparative Example 3)

The experiment was conducted in the same manner as in Example 1 except that 3 parts by weight of triacrylate of trimethylolpropane triglycidyl ether was added instead of 3 parts by weight of a hydrophilic epoxy diacrylate compound including an amine group, but the aqueous solution of sodium acrylate was insufficient due to lack of hydrophilicity. It was not possible to continue the experiment.

The experimental results of the above Examples and Comparative Examples are summarized in Table 1 below.

division Example 1 Example 2 Example 3 Comparative Example 1 Comparative Example 2 Mixed viscosity (cps) 5 6 5 5 5 Curing time (seconds) 120 110 130 420 140 Elongation (%) 400 370 520 1200 1100 Tensile Strength (N / mm ² ) 1.6 1.8 1.3 0.4 0.5 Tensile Shear Adhesion Strength (N / mm ² ) 0.8 0.7 0.7 0.1 0.1 Permeability coefficient (cm / S) 1.0x10 ^-9 1.1x10 ^-9 1.2 x 10 ^-9 8.0x10 ^-9 1.2 x 10 ^-9

As is well shown in the experimental results of the above Examples and Comparative Examples, the effect of using a hydrophilic epoxy diacrylate compound containing an amine group as the crosslinking agent is obvious.

As described above, the acrylate-based water repellent agent according to the present invention has excellent environmental friendliness, and is a water repellent agent that can satisfy various physical properties such as curing time and strength required for the water repellent and order coefficient, and is relatively easy and economical. Another advantage is that it can be manufactured by the method.

Claims (4)

Persulfate compound and amine compound are added to the acrylate compound as redox polymerization catalyst to form hydrous hydrogel, which is used for the order and reinforcement of underground foundations and index of concrete structures in tanks, tunnels and sewer pipes in civil engineering and building construction. In the acrylate-based ordering agent, The acrylate compound is an acrylate-based water-ordering agent, characterized in that the acrylic acid metal salts prepared by adding acrylic acid and methacrylic acid to a metal hydroxide aqueous solution and a hydrophilic epoxy diacrylate compound containing an amine group as a crosslinking agent. The acrylate type according to claim 1, wherein the hydrophilic epoxy diacrylate compound including the amine group is prepared by a 1: 1 molar ratio Michael Addition of an epoxy triacrylate compound and a secondary amine compound. Order system. The group according to claim 2, wherein the epoxy triacrylate compound is composed of triacrylate of trimethylolpropanetriglycidyl ether, triacrylate of glycerol triglycidyl ether, sorbitol triglycidyl ether triacrylate, and a mixture thereof. An acrylate-based water repellent, characterized in that any one or more selected from. The compound according to claim 2, wherein the secondary amine compound is selected from the group consisting of diethylamine, dipropylamine, dibutylamine, methylethanolamine, ethylethanolamine, diethanolamine, dicyclonuxylamine, and mixtures thereof. An acrylate-based water-order agent, characterized in that any one or more.