KR101940026B1 - Method for preparing polymer for concrete modification and concrete composition containing polymer produced by the method - Google Patents

Abstract

The present invention relates to a manufacturing method of a concrete reforming polymer and a concrete composite including the same. To this end, the concrete reforming polymer comprises: a polymer polymerized by using ethenyl acetate and ethyl prop-2-enoate; and propylene dicarboxylic acid which is branched on a surface of the polymer particle. The manufacturing method of the concrete reforming polymer provides good polymer dispersion and storage stability.

Description

BACKGROUND OF THE INVENTION 1. Field of the Invention [0001] The present invention relates to a method for producing a concrete-modified polymer, and a concrete composition comprising the polymer produced by the method. BACKGROUND OF THE INVENTION < RTI ID =

The present invention relates to a method for producing a polymer for concrete modification and a concrete composition comprising the polymer produced by the method. More particularly, the present invention relates to a concrete composition comprising a mixture of ethylene propyl-2-enoate -enoate), and a concrete composition comprising the polymer produced by the method.

Generally, a fast-curing or high-strength cement-based composition is a concrete road in which a quick-repair is required in the form of a composition containing a very fast or rigid cement itself and a compounding water, a rapid or rigid cement, silica sand, sand, aggregate, And buildings are applied to quickly repair and repair. However, even when the amount of unit cement is controlled by the composition of the quick-curing or high-strength cement-based composition, the water resistance and durability of the composition itself are limited.

The reason for this is that the quick or rigid cement composition itself is more water-absorbing than waterproof and repeatedly shrinks and expands according to changes in the atmospheric temperature. In this process, there is a difference in shrinkage relaxation ratio with the adhesive matrix , The initial bonding state is loosened due to the stress generated at the bonding interface, leading to local or total interface detachment or cracking, and leakage and life cycle of the quick-curing cement composition due to external inflow water or moisture penetrated into the defect There was an issue that was shortened.

In order to solve the above problems, the use of latex modified concrete in which SBR (Styrene-Butadiene Rubber) latex is added to concrete repair and reinforcement work is described in Korean Patent Registration No. 421255.

According to the above description, when SBR (Styene-Butadine Rubber) latex is used to produce modified quick-hard and high-strength concrete, when the temperature of the next year increases due to the freezing and thawing resistance in the winter season, Respectively. This phenomenon is caused by the deterioration of the water resistance and the resistance to chloride of SBR latex. Therefore, it has been limited to guarantee concrete durability.

In the present invention, propylene dicarboxylic acid is branched on the surface of polymer particles obtained by polymerizing ethenyl acetate and ethyl prop-2-enoate as main monomers, It is a principal object of the present invention to provide a method for producing a polymer for concrete modification, which is excellent in chemical conversion, and which is obtained by dividing propylene dicarboxylic acid by reaction time, and thus has excellent dispersion and storage stability of the polymer.

delete

It is another object of the present invention to provide a concrete composition improved in waterproofness, compressive strength and adhesion strength by mixing the concrete composition with the above-mentioned concrete modifying polymer in a concrete composition.

In order to accomplish the above object, the present invention provides a method for preparing an emulsifier composition, which comprises the steps of: 0.1 to 0.5 parts by weight of sodium lauryl sulfate; 0.3 to 0.5 parts by weight of cetyl alcohol; and 0.1 to 0.3 parts by weight of sodium carbonate;
After the emulsifier composition was added, the temperature was raised to 60 ° C., 35 to 45 parts by weight of ethynyl acetate as a reaction monomer and 55 to 65 parts by weight of ethyl prop-2-enoate were added Next, 0.1 to 0.3 parts by weight of benzoyl peroxide is further added to initiate the reaction.
When the reaction is initiated, 1 to 5 parts by weight of propylene dicarboxylic acid, which is a functional monomer, is added, and 20 to 40% of the total amount of the propylene dicarboxylic acid is introduced during the initial 4 hours from the end of the reaction for 9 hours, A propylene dicarboxylic acid addition step of charging the remainder for a period of time;
And 0.2 to 0.3 parts by weight of sodium sulfoxylate formaldehyde, which is a reaction terminator, is added 1 hour before the completion of the reaction to complete the reaction.
Also, the present invention provides a method for producing a reinforced concrete, comprising: 0.01 to 5 parts by weight of a concrete modification polymer produced according to the first aspect; 15 to 20 parts by weight of a cement binder; 25 to 45 parts by weight of fine aggregate or silica sand; 25 to 40 parts by weight of a coarse aggregate, and 0.03 to 10 parts by weight of a blend;
Wherein the cement binder is a ultra fast cement binder or an aged steel cement binder;
20 to 50 parts by weight of crude steel cement, 20 to 50 parts by weight of calcium sulfoaluminate cement, 20 to 50 parts by weight of alumina cement, 5 to 15 parts by weight of gypsum and 0.01 to 1.0 part by weight of a coagulation retardant, ;
In the case of the above-mentioned prepreg steel cement binder, 30 to 40 parts by weight of Portland cement, 20 to 50 parts by weight of calcium sulfoaluminate cement, 20 to 50 parts by weight of alumina cement, 5 to 15 parts by weight of gypsum, The present invention also provides a concrete composition comprising a polymer for reforming concrete.

delete

delete

delete

delete

delete

delete

delete

The polymer for concrete modification according to the present invention having the above-mentioned structure has an effect of improving stability of polymer itself and miscibility with cement due to anionic functional groups of functional monomers branched on the surface of polymerized polymer particles.

In addition, in the method for producing such a concrete-modifying polymer, an anionic functional group can be imparted to the inside and the surface of the polymer particle by adding the propylene dicarboxylic acid, which is a functional monomer, by the reaction time, And the dispersion and storage stability of the polymer produced after the polymerization can be improved.

In addition, the above-mentioned concrete modifying polymer can be applied to fast-curing or high-strength cement having different powdery degree, and when mixed with a concrete composition, the mixing ratio of cement and the amount of unit cement used in the concrete composition can be reduced Economical efficiency and cost saving effect, and water resistance and durability can be greatly improved.

Hereinafter, preferred embodiments of the present invention will be described in detail with reference to the drawings. However, it should be understood that the following embodiments are provided so that those skilled in the art may understand the present invention without departing from the scope and spirit of the present invention. It is not.

The polymer for concrete modification according to one embodiment of the present invention is a polymer obtained by polymerizing ethenyl acetate and ethyl prop-2-enoate; And propylene dicarboxylic acid branched at the particle surface of the polymer.

It is preferable that the ethenyl acetate is 35 to 45 parts by weight, the ethyl prop-2-enoate is 55 to 65 parts by weight, and the propylene dicarboxylic acid is 1 to 5 parts by weight .

According to another aspect of the present invention, there is provided a method of preparing a polymer for modifying concrete, comprising: injecting an emulsifier composition; Introducing a reaction monomer to initiate a reaction; Introducing a functional monomer; And terminating the reaction by injecting the reaction termination.

The step of introducing the emulsifier composition may be a step of injecting sodium lauryl sulfate, cetyl alcohol, and sodium carbonate, which are emulsifier compositions, before the polymerization reaction. At this time, it is preferable to add 0.1-0.5 parts by weight of sodium lauryl sulfate, 0.3-0.5 parts by weight of cetyl alcohol and 0.1-0.3 parts by weight of sodium carbonate, but it is not limited thereto.

The step of initiating the reaction may be a step of initiating the reaction by injecting ethynyl acetate and ethyl prop-2-enoate, which are reaction monomers.

Specifically, after the emulsifier composition was added, the temperature was raised to 60 ° C, and 35 to 45 parts by weight of ethynyl acetate as a reaction monomer and 55 to 65 parts by weight of ethyl prop-2-enoate To initiate the reaction.

The above-mentioned ethenyl acetate (molecular weight 86 ± 0.1 g / mol) functions to impart and control the stiffness of the formed film mattress, thereby enhancing and controlling the compressive strength of the polymer-incorporated cement and concrete composition. If the amount of the injected ethenyl acetate is less than 35 parts by weight, the film mattress becomes softer and the compressive strength is lowered. When the amount exceeds 80 parts by weight, the film mattress becomes stiff and the brittleness of the cement and concrete composition becomes strong, The problem becomes weak.

The ethyl prop-2-enoate (molecular weight 100 ± 0.1 g / mol) has a function of absorbing the ductility and external impact of the formed film mattress, and the polymer-incorporated cement and concrete composition To increase the flexural strength and tensile strength of the steel sheet. When the amount of the ethyl prop-2-enoate added is less than 55 parts by weight, the film mattress becomes stiff to lower the flexural strength and tensile strength of the cement and concrete composition. When the amount of ethyl prop-2-enoate is more than 65 parts by weight The film mattress is excessively softened so that the flexural strength and tensile strength of the cement and concrete composition are improved but the compressive strength is significantly reduced.

As described above, ethylenevacetate and ethyl prop-2-enoate form a main chain through a polymerization reaction. If the ethylenevprop-2-enoate is mixed with a cement and a concrete system, the interface between the cement and the concrete particles Can be filled with a continuous film mattress to impart water resistance to the cement and concrete composition and improve corrosion resistance to external influent and compounds.

On the other hand, it is preferable to add benzoyl peroxide as a reaction initiator at the start of the reaction, but it is not limited thereto, and 0.1 to 0.3 parts by weight of the reaction initiator is preferably added.

Then, when the reaction is initiated, 1 to 5 parts by weight of propylene dicarboxylic acid (molecular weight 130 ± 0.1 g / mol), which is a functional monomer, is added. It is preferable that 20 to 40%, preferably 30% of the total charged amount is charged at the beginning of the reaction and 60 to 80%, preferably 70% of the total charged amount, is added at the end of the reaction. Specifically, 30% of 1 to 5 parts by weight of propylene dicarboxylic acid may be added for 4 hours, and 70% may be added for 4 hours during 5 hours of the remaining reaction time. However, the present invention is not limited thereto.

By adding the propylene dicarboxylic acid divided by the reaction time, anionic functional groups can be imparted to the inside and the surface of the polymer particle, the polymerization rate of the monomer can be maintained uniformly, and the dispersion and storage stability of the polymer Can be improved.

The propylene dicarboxylic acid serves to improve dispersion stability and storage stability between particles on the surface of the polymerized polymer and improves miscibility by neutralizing the polyvalent cation on the surface of the cement and concrete particles when mixing the cement and concrete composition It plays a role. In addition, the propylene dicarboxylic acid is anionically charged on the surface of the polymerized polymer particles, and when the member of the cement composition is a concrete, the propylene dicarboxylic acid bonds with the cement component of the cation component of the surface of the member to improve the adhesive strength of the cement composition, Thereby improving the adhesion strength between the two compositions.

When the amount of the propylene dicarboxylic acid is less than 1 part by weight, the dispersion stability and storage stability of the polymerized polymer are decreased. When the amount of the propylene dicarboxylic acid is more than 5 parts by weight, the anionically charged layer on the polymer particle surface becomes excessively high, A problem occurs.

Then, 0.2 to 0.3 part by weight of sodium sulfoxylate formaldehyde, which is a reaction terminator, is added 1 hour before the end of the reaction to terminate the reaction.

The ethyl prop-2-enoate polymer for concrete modification, prepared as described above, can be applied to fast-curing or high-strength cements having different degrees of powder, When used in combination, the waterproofness and durability of the concrete composition can be improved.

The concrete composition according to one embodiment of the present invention includes the concrete reforming polymer; Cement binder; Fine aggregate or silica sand; Coarse aggregate and the number of the formulations.

The concrete modifying polymer is preferably used in an amount of 0.01 to 5 parts by weight. When the amount is less than 0.01 part by weight, the required water resistance within the predetermined mixing amount range of the unhardened concrete can not be obtained, and further compounding water is required for securing the dispersibility and the long-term durability is deteriorated due to the decrease in strength and waterproofness. On the other hand, if the amount of the non-hardened concrete exceeds 5 parts by weight, the viscosity of the unhardened concrete is excessively increased and the flatness and the surface finish of the concrete become poor.

20-30 parts by weight of crude steel cement, 20-50 parts by weight of calcium sulfoaluminate cement, 20-50 parts by weight of alumina cement, 5-15 parts by weight of gypsum, 0.01-0.5 parts by weight of a coagulation retardant, Preferably 1.0 part by weight.

When the cement binder is an aged steel cement binder, 30 to 40 parts by weight of Portland cement, 20 to 50 parts by weight of calcium sulfoaluminate cement, 20 to 50 parts by weight of alumina cement, 5 to 15 parts by weight of gypsum, Preferably 0.01 to 1.0 part by weight.

The crude steel cement is preferably one specified in KS. If the amount of the crude steel cement is less than 20 parts by weight, the initial strength development is delayed. If the amount is more than 30 parts by weight, the amount of the compounding water is increased and the amount of alumina cement and gypsum added is decreased.

The Portland cement is a cement satisfying the KS L 5201 quality standard. When the amount of the Portland cement is less than 30 parts by weight, the content of calcium sulfoaluminate and alumina cement increases, And the strength due to the increase in the number of concrete formulations is lowered. If the amount of the portland cement is more than 40 parts by weight, the amount of concrete blended is reduced and the dispersibility is improved, but it becomes difficult to secure initial strength.

When the amount of the calcium sulfoaluminate cement is less than 20 parts by weight, the initial strength development rate is slowed and the viscosity of the concrete is decreased, so that it becomes difficult to secure the material separation and flatness. If the amount is more than 50 parts by weight, it is necessary to increase the number of concrete blends. As a result, the initial strength of the concrete is lowered. On the contrary, the long-term strength is greatly increased and the brittleness of the final concrete is increased.

When the amount of the alumina cement is less than 20 parts by weight, the viscosity of the concrete deteriorates and the initial strength development hardly reaches the reference value. When the amount of the alumina cement is more than 50 parts by weight, And the initial strength is excellent, but the long-term strength exceeds the reference value.

The gypsum is used for the freshness, coagulation and initial strength development of concrete and anhydrous gypsum is used. If the content of the gypsum is less than 5 parts by weight, the coagulation delay is delayed and it is difficult to secure the pot life. If the content of the gypsum exceeds 15 parts by weight, the initial strength is lowered due to excessive coagulation delay.

The coagulation retarder is used to control the retention time of concrete, and anhydrous or functional citric acid is used as the coagulation retarder. The amount to be used is 0.01-1.0 parts by weight, and the amount to be used is adjusted depending on the atmospheric temperature. In the winter, 0.01-0.3 parts by weight and in the summer, 0.4-1.0 parts by weight is used. If the amount is more than 1.0 part by weight, the initial strength of the concrete is delayed and the opening time becomes difficult to secure.

On the other hand, if necessary, the cement binder may further contain calcium sulphoaluminate expanding agent, high performance water reducing agent, thickening agent, and the like, but is not limited thereto.

The cement binder is preferably used in an amount of 15-20 parts by weight of the concrete composition of the present invention. If the amount is less than 15 parts by weight, the viscosity of the unhardened concrete may be insufficient and the possibility of bleeding may increase, thereby increasing the possibility of plastic cracking. In addition, the strength and watertightness of the concrete reduces the permeability due to the decrease in watertightness. On the contrary, when the amount exceeds 20 parts by weight, it is difficult to control the workability and the pot life due to the viscosity increase due to overuse of the cement binder, and drying shrinkage crack due to excessive water tightness may occur.

The fine aggregate has a particle size of 5 mm or less and can be used without limitation if it satisfies the standard specification standard of concrete. If the amount of the fine aggregate is less than 25 parts by weight, the flatness of the concrete surface becomes poor. , The strength of the concrete is lowered, and the amount of the fine aggregate used is preferably 25-45 parts by weight.

The silica sand is a powder of super fine particles in a fine powder state containing silica (SiO ₂ ) component, which is anhydrous silicic acid. It fills the pores in the concrete and induces hydration reaction in the long term through hydration reaction with the compound water. It strengthens the watertightness of concrete and improves waterproofing, thereby enhancing the durability of the concrete. When the amount of the silica sand is less than 25 parts by weight, the flatness of the concrete surface becomes poor. When the amount of the silica sand is more than 45 parts by weight, the strength of the concrete is lowered.

The coarse aggregate has a particle size of about 19 mm and satisfies the standard value of concrete standard specifications. If the amount of the coarse aggregate is less than 25 parts by weight, the strength of the concrete is lowered. If the coarse aggregate exceeds 40 parts by weight, Resulting in poor performance and flatness. Therefore, the amount of the coarse aggregate is preferably 25-40 parts by weight.

Hereinafter, preferred embodiments of the concrete modifying polymer and the concrete composition according to the present invention will be described in more detail with reference to the drawings. However, it should be understood that the following embodiments are provided so that those skilled in the art may understand the present invention without departing from the scope and spirit of the present invention. It is not.

≪ Preparation Example 1 &

0.2 part by weight of sodium lauryl sulfate, 0.3 part by weight of cetyl alcohol and 0.1 part by weight of sodium carbonate were charged into the reactor, and after the temperature of the reactor was raised by 60 (+/- 3) DEG C, the main monomer, 35 parts by weight of ethyl acetate (molecular weight 86 ± 0.1 g / mol) and 65 parts by weight of ethyl prop-2-enoate (molecular weight 100 ± 0.1 g / mol) At the same time as the initiation of the polymerization reaction, 30% of 3 parts by weight of propylene dicarboxylic acid (molecular weight 130 ± 0.1 g / mol) was added for 4 hours and the remaining 70% was added for 4 hours during 5 hours, 0.3 part by weight of sulfoxylated formaldehyde was added 1 hour before the end of the reaction to terminate the reaction to prepare a concrete reforming polymer.

≪ Preparation Example 2 &

Except that 40 parts by weight of ethenyl acetate as a main monomer and 60 parts by weight of ethyl prop-2-enoate were added, respectively, to prepare a concrete reforming polymer .

≪ Preparation Example 3 &

Except that 45 parts by weight of ethenyl acetate as a main monomer and 55 parts by weight of ethyl prop-2-enoate were added, respectively, and 1 part by weight of propylene dicarboxylic acid was added. The polymer for concrete modification was prepared through the same procedure as in Example 1.

≪ Preparation Example 4 &

Except that 40 parts by weight of ethenyl acetate as a main monomer and 56 parts by weight of ethyl prop-2-enoate were added and propylene dicarboxylic acid was not added. The concrete modification polymer was prepared by the same procedure as the above.

The physical properties of the concrete-modifying polymers prepared according to Examples 1 to 4 are shown in Table 1 below.

division Average particle size ¹⁾
(nm) pH ²⁾
Solid concentration ³⁾
(%) Viscosity ⁴⁾
(mPa.s) Production Example 1 205 8.7 48.1 83 Production Example 2 201 8.5 47.7 90 Production Example 3 198 8.6 47.8 98 Production Example 4 160 8.9 47.8 211

1) KSA ISO 13320-2014

2) KSM 6516-2016

3) KSM 6516-2016

4) KSM 6516-2016 (Brookfield viscometer, LV1, 30 r / min)

As shown in Table 1, the concrete-modifying polymers of Production Examples 1 to 3 produced by the production method of the present invention showed similar particle size, pH, solid content concentration and viscosity, while Production Example 4 showed that propylene dicarboxylic acid It was found that the particle size of the polymerized polymer was small and the dispersion repulsion between the polymer particles was small and the viscosity was relatively high.

≪ Examples 1 to 4 >

The cement-based quick-setting binder, the fine aggregate and the coarse aggregate were weighed and weighed into a forced mixing mixer under the conditions shown in Table 2 below, and then mixed for 3 minutes under dry conditions. The improvement polymer and the compounding water were simultaneously added and mixed for 1 minute and 30 seconds to prepare a concrete composition.

The quick-setting cement binder was prepared by mixing 30 parts by weight of crude steel cement, 30 parts by weight of CSA, 20 parts by weight of alumina cement, 10 parts by weight of gypsum, 0.5 parts by weight of CSA swelling agent, 0.1 parts by weight of lithium camomone, 0.01 parts by weight of a high-performance water reducing agent, 0.01 parts by weight of a thickener, and 0.01 parts by weight of an internal retardant were mixed. The physical properties of the cement latex binder are shown in Table 3 below.

≪ Comparative Example 1 &

As shown in Table 2 below, a concrete composition was prepared through the same procedure as in Example 1, except that the polymer for improving concrete was not mixed.

division Unit quantity (kg / m ³ ) Number of ingredients cement Fine aggregate Coarse aggregate Polymer Examples 1 to 4 90 340 929 801 87 Comparative Example 1 132 ^* 340 929 801

*: According to the slump 160 mm of the above-mentioned quick-speed cement binder, Comparative Example 1 requires an additional compounding amount

Tests / Test Items unit Test Methods Measures importance g / cm ³ KSL 5110: 2016 2.9 Minutes cm ² / g KSL 5201: 2016 5897 Setting time Superfine minute 30 End Hours: Minutes 0:51 Stability (autoclave) % 0.08 Compressive strength 4 hours MPa 30.7 28th 49.5

The polymer-modified concrete composition prepared according to Examples 1 to 4 and the concrete composition prepared according to Comparative Example 1 were measured for water absorption according to the test method specified in KS F 4004, and the results are shown in Table 4 below.

As shown in Table 4 below, the water absorption rate of Examples 1 to 4 was significantly lower than that of Comparative Example 1, and the water absorption rate of Example 4 was lower than those of Examples 1 to 3. When the water absorption rate is high, the absorption of external inflow water increases at the summer season and the infiltration and diffusion of the infiltration into the concrete structure is increased, so that the neutralization of the concrete progresses rapidly and the inflation of infiltrated inflow water And floating phenomenon occurs, which causes defects.

division unit Example 1 Example 2 Example 3 Example 4 Comparative Example 1 Absorption rate % 0.4 0.3 0.3 0.2 4.5

Also, the polymer-modified concrete composition prepared according to Examples 1 to 4 and the concrete composition prepared according to Comparative Example 1 were measured for their salt penetration resistance according to the method defined in KS F 2711. The results are shown in Table 5 Respectively.

As can be seen from the following Table 5, it can be seen that Examples 1 to 4 have significantly lower salt infiltration than Comparative Example 1.

division unit Example 1 Example 2 Example 3 Example 4 Comparative Example 1 Salt penetration resistance coulomb 658 652 650 653 2530

The polymer-modified concrete composition prepared according to Examples 1 to 4 and the concrete composition prepared according to Comparative Example 1 were subjected to compression strength (after 4 hours of curing) and adhesion of the concrete composition according to the method specified in KS F 2405 and KS F2762 The intensity (28 days old) was measured and the results are shown in Table 6 below.

As shown in Table 6 below, Examples 1 to 4 showed higher compressive strength than Comparative Example 1, and these results show that Examples 1 to 4 are excellent in miscibility with ultrafast cement of fine powder It was found that normal compression strength was achieved. In addition, also in the result of the adhesion strength, Examples 1 to 4 exhibited higher interfacial adhesion strength than Comparative Example 1.

division unit Example 1 Example 2 Example 3 Example 4 Comparative Example 1 Compressive strength MPa 23.5 23.8 22.3 22.6 19.6 Bond strength 1.87 1.85 1.91 1.90 0.94

≪ Examples 5 to 8 >

Agitated steel cement binder, fine aggregate and coarse aggregate were weighed and weighed into a forced mixing mixer under the mixing conditions shown in Table 7 below, and then mixed for 3 minutes under the dry mixing condition. Then, each of the concrete prepared in Production Examples 1 to 4 The improvement polymer and the compounding water were simultaneously added and mixed for 1 minute and 30 seconds to prepare a concrete composition.

The autoclaved cement binder was prepared by mixing 35 parts by weight of portland cement, 25 parts by weight of CSA, 25 parts by weight of alumina cement, 8 parts by weight of gypsum, 0.4 part by weight of CSA swelling agent, 0.01 part by weight of a coagulation retarder, 0.01 part by weight of high- And 0.01 part by weight of a thickener were mixed and used. The properties of the hardened cement based binder are shown in Table 8 below.

≪ Comparative Example 2 &

As shown in Table 7 below, a concrete composition was prepared through the same procedure as in Example 5 except that the polymer for improving concrete was not mixed.

division Unit quantity (kg / m ³ ) Number of ingredients cement Fine aggregate Coarse aggregate Polymer Examples 5 to 8 90 340 929 801 87 Comparative Example 2 132 ^* 340 929 801

*: Based on slump 160 mm of the above-mentioned cold-rolled steel cement-based material, Comparative Example 2 requires additional compounding amount

Tests / Test Items unit Test Methods Measures importance g / cm ³ KSL 5110: 2016 2.94 Minutes cm ² / g

KSL 5201: 2016 5320 Setting time Fresh minute 50 closing Hours: Minutes 1: 10 Stability (autoclave) % 0.07 Compressive strength 12 hours MPa 28.7 28th 45.5

The polymer-modified concrete composition prepared according to Examples 5 to 8 and the concrete composition prepared according to Comparative Example 2 were measured for water absorption according to the test method specified in KS F 4004, and the results are shown in Table 9 below.

As shown in Table 9 below, Examples 5 to 8 showed higher water resistance than Comparative Example 2, and Examples 5 to 8 had similar absorption rates.

division unit Example 5 Example 6 Example 7 Example 8 Comparative Example 2 Absorption rate % 0.5 0.4 0.4 0.4 5.2

The polymer-modified concrete composition prepared according to Examples 5 to 8 and the concrete composition prepared according to Comparative Example 2 were measured for their salt penetration resistance according to the method defined in KS F 2711. The results are shown in Table 10 Respectively.

As can be seen from the following Table 10, in Examples 5 to 8, the salinity infiltration was very low compared to Comparative Example 2, and in Examples 5 to 8, the pores in the grained steel cement composition were filled with the polymer film This is interpreted as a result of suppressing the infiltration of external influent.

division unit Example 5 Example 6 Example 7 Example 8 Comparative Example 2 Salt penetration resistance coulomb 835 840 838 841 2850

The polymer-modified concrete composition prepared according to Examples 5 to 8 and the concrete composition prepared according to Comparative Example 2 were subjected to compression strength (after 12 hours of curing) and adhesion of the concrete composition according to the method specified in KS F 2405 and KS F2762, Strength (28 days old) was measured and the results are shown in Table 11 below.

As shown in the following Table 11, Examples 5 to 8 were superior in compressive strength to Comparative Example 2, and these results show that Examples 5 to 8 are excellent in miscibility due to lubrication action between the hardened steel cement particles It was confirmed that the amount of compounding required to obtain the same slump is less than that of Comparative Example 2, and that Comparative Example 2 requires an additional amount of compounding than that of Examples 5 to 8 in order to obtain a slump of the same condition. As a result, it was found that the compressive strength of the rough-textured cement composition prepared in Comparative Example 2 was lower than that of Examples 5 to 8.

In addition, the tendency of the above results can be confirmed from the results of the adhesion strength test. In the case of the grained concrete cement compositions using Examples 5 to 8, the amount of blending required to obtain the slump of the target concrete was required to be comparatively less than 2 in comparison, showing the difference in the adhesion of the adhesive interface.

division unit Example 5 Example 6 Example 7 Example 8 Comparative Example 2 Compressive strength MPa 22.5 23.1 22.8 23.0 16.7 Bond strength 1.64 1.60 1.68 1.65 0.83

≪ Examples 9 to 12 >

The cement paste material, silica sand and coarse aggregate were weighed and weighed at a rapid mixing speed under the conditions shown in Table 13 below. The resulting mixture was charged into a forced mixing mixer and mixed for 3 minutes under dry conditions. The improvement polymer and the compounding water were simultaneously added and mixed for 1 minute and 30 seconds to prepare a quick hard mortar concrete composition.

The fast-curing cement binder used was a binder having physical properties shown in Table 3, and the silica sand was mixed with quartz particles containing a silicon dioxide component, which was anhydrous silicic acid, at the composition ratios shown in Table 12 below.

≪ Comparative Example 3 &

As shown in the following Table 13, a quick-setting mortar concrete composition was prepared through the same procedure as in Example 9, except that the polymer for improving concrete was not mixed.

division Mesh mm Composition ratio No. 3 8-12 2.36-1.70 One No. 5 20-40 0.85-0.42 One No. 6 40-70 0.42-0.22 One

division Unit quantity (kg / m ³ ) Number of ingredients cement Silica sand Coarse aggregate Polymer Examples 9 to 12 92 340 929 801 87 Comparative Example 3 134 ^* 340 929 801

*: Based on the slump 160 mm of the above-described quick mortar mortar concrete binder, Comparative Example 3 requires an additional compounding amount

The water absorption rate of the polymer-modified quick-setting mortar concrete composition prepared according to Examples 9 to 12 and the fast-setting mortar concrete composition prepared according to Comparative Example 3 was measured according to the test method defined by KS F 4004, Table 14 shows the results.

As shown in the following Table 14, the absorption rates of Examples 9 to 12 were lower than those of Comparative Example 3. As a result, it was confirmed that the concrete compositions of Examples 9 to 12, which were uniformly formed in the inner voids of the quick hard mortar concrete produced by using silica sand instead of the fine aggregate, had better water resistance than Comparative Example 3.

division unit Example 9 Example 10 Example 11 Example 12 Comparative Example 3 Absorption rate % 0.4 0.4 0.3 0.3 4.8

The salt permeation resistance of the polymer-modified quick-setting mortar concrete composition prepared according to Examples 9 to 12 and the fast-setting mortar concrete composition prepared according to Comparative Example 3 was measured according to the method defined in KS F 2711, The results are shown in Table 15 below.

As can be seen from the following Table 15, Examples 9 to 12 showed superior salt penetration resistance to Comparative Example 3.

division unit Example 9 Example 10 Example 11 Example 12 Comparative Example 3 Salt penetration resistance coulomb 541 548 554 550 2035

In addition, the polymer-modified quick-release mortar concrete composition prepared according to Examples 9 to 12 and the quick-hard mortar concrete composition prepared according to Comparative Example 3 were subjected to compression strength (curing 4 hours later) and adhesion strength (28 days old) were measured, and the results are shown in Table 16 below.

As shown in Table 16 below, Examples 9 to 12 confirmed the results of Comparative Compression 3 having excellent compressive strength, and these results show that Examples 9 to 12 are comparable to Comparative Example 3 in the manufacture of the same quick hardening mortar concrete , And it was possible to reduce the mixing amount of the fast-setting mortar concrete composition through the lubrication action between the constituents of the fast-hard mortar concrete composition of Examples 9 to 12 above.

These results showed similar tendency in the adhesion strength test, and it was found that the reduction in the amount of blending was effective in increasing the compressive strength and the adhesion strength in the manufacture of the quick hard mortar concrete using Examples 9 to 12.

division unit Example 9 Example 10 Example 11 Example 12 Comparative Example 3 Compressive strength MPa 24.3 24.8 24.7 24.8 20.1 Bond strength 1.73 1.76 1.74 1.70 0.89

While the present invention has been particularly shown and described with reference to exemplary embodiments thereof, it is to be understood that the invention is not limited to the disclosed exemplary embodiments, This is possible.

Claims (8)

0.1 to 0.5 parts by weight of sodium lauryl sulfate, 0.3 to 0.5 parts by weight of cetyl alcohol, and 0.1 to 0.3 parts by weight of sodium carbonate;
After the emulsifier composition was added, the temperature was raised to 60 ° C., 35 to 45 parts by weight of ethynyl acetate as a reaction monomer and 55 to 65 parts by weight of ethyl prop-2-enoate were added Next, 0.1 to 0.3 parts by weight of benzoyl peroxide is further added to initiate the reaction.
When the reaction is initiated, 1 to 5 parts by weight of propylene dicarboxylic acid, which is a functional monomer, is added, and 20 to 40% of the total amount of the propylene dicarboxylic acid is introduced during the initial 4 hours from the end of the reaction for 9 hours, A propylene dicarboxylic acid addition step of charging the remainder for a period of time;
And 0.2 to 0.3 parts by weight of sodium sulfoxylate formaldehyde, which is a reaction terminator, is added 1 hour before the completion of the reaction, thereby terminating the reaction.
0.01 to 5 parts by weight of a concrete-modifying polymer prepared according to claim 1; 15 to 20 parts by weight of a cement binder; 25 to 45 parts by weight of fine aggregate or silica sand; 25 to 40 parts by weight of a coarse aggregate, and 0.03 to 10 parts by weight of a blend;
Wherein the cement binder is a ultra fast cement binder or an aged steel cement binder;
20 to 50 parts by weight of crude steel cement, 20 to 50 parts by weight of calcium sulfoaluminate cement, 20 to 50 parts by weight of alumina cement, 5 to 15 parts by weight of gypsum and 0.01 to 1.0 part by weight of a coagulation retardant, ;
In the case of the above-mentioned prepreg steel cement binder, 30 to 40 parts by weight of Portland cement, 20 to 50 parts by weight of calcium sulfoaluminate cement, 20 to 50 parts by weight of alumina cement, 5 to 15 parts by weight of gypsum, Wherein the reinforcing material is a reinforcing material. delete delete delete delete delete delete