KR102493595B1 - Additive composition for cement - Google Patents

Abstract

상기 화학식 1에서,
R₁, R₂ 및 R₃는 서로 독립적으로 수소 또는 하이드록시(C₁-C₆)알킬이고, 단 R₁, R₂ 및 R₃ 모두가 수소인 경우는 제외되고,
화학식 2

상기 화학식 2에서,
R₄ 및 R₅는 서로 독립적으로 수소 또는 하이드록시(C₁-C₆)알킬이고,
R₆은 하이드록시(C₁-C₆)알킬이고,
Z는 (C₁-C₆)알킬렌이다.The present invention relates to a novel cement additive composition for improving the compressive strength properties of mortar or concrete. Specifically, a cement additive composition comprising a compound of Formula 1 and a compound of Formula 2 below is provided.
Formula 1

In Formula 1,
R ₁ , R ₂ and R ₃ independently of each other are hydrogen or hydroxy(C ₁ -C ₆ )alkyl, except when R ₁ , R ₂ and R ₃ are all hydrogen;
Formula 2

In Formula 2,
R ₄ and R ₅ independently represent hydrogen or hydroxy(C ₁ -C ₆ )alkyl;
R ₆ is hydroxy(C ₁ -C ₆ )alkyl;
Z is (C ₁ -C ₆ )alkylene.

Description

Cement additive composition {ADDITIVE COMPOSITION FOR CEMENT}

The present invention relates to a cement additive composition having excellent cement grinding ability and improving compressive strength properties of mortar or concrete.

In the cement manufacturing process, ore raw materials such as limestone, silica stone, clay, iron ore, and slag containing a large amount of calcium carbonate (CaCO ₃ ) are pulverized and then heat treated at a high temperature of about 1400 degrees. Hardened nodules called clinkers are formed. After cooling the clinker, a small amount of gypsum (CaSO ₄ ) is added in a grinding mill and pulverized with a ball mill or roller mill by a wet or dry method to obtain a uniform powder product known as Portland cement. The purpose of pulverizing clinker and gypsum in the cement manufacturing process is to increase the surface area of cement clinker to increase reactivity, to make fine particles easier, and to increase the mixing effect and bonding strength with sand or gravel. The final performance of the product in this process this is decided

When clinker is pulverized into fine particles, ionic bonds are destroyed by mechanical processes, resulting in positive and negative charges on the surface of newly formed particles, and aggregation occurs due to electrostatic attraction between particles. This greatly reduces the grinding efficiency and greatly increases energy consumption.

The cement clinker crushing process is an important process that consumes 60-70% of the total energy in the cement production process. Therefore, grinding aids are used as additives for the purpose of increasing grinding efficiency for energy saving. Recently, functional grinding aids that have not only grinding efficiency but also an effect of increasing compressive strength when manufacturing mortar or concrete are in the spotlight.

Regarding the above grinding aids, U.S. Patent Nos. 4,943,323 and 6,290,772 of W.R Grace of the United States of America disclose grinding containing triisopropanolamine (TIPA) for improving productivity, reducing energy costs and improving grinding performance. The preparation is described, and a method of using TIPA as a grinding aid by partially mixing triethanolamine (TEA) with it is also disclosed. Japanese Patent Laid-open Publication No. 1998-324550 and Korean Patent Registration No. 10-0596507 disclose additives for grinding aid containing compounds in which TEA and TIPA are substituted with acetic acid or a carboxyl group having 2 to 4 carbon atoms, a sulfate, or an ester group. Korean Patent Registration No. 10-0650135 discloses an additive for grinding aid in which glycol and alkanolamine are mixed with polypropyleneethanolamine.

However, due to recent environmental issues, the ratio of clinker among cement components (clinker, gypsum, limestone, slag, etc.) is decreasing in order to reduce carbon emissions. As a result, there is a problem of reducing the initial strength of cement. Alternatively, there is an increasing demand for functional cement additives that improve the compressive strength properties of concrete.

US Patent No. 4,943,323 (1990.07.24) US Patent No. 6,290,772 (2001.09.18) Japanese Patent Laid-Open No. 1998-324550 (1998.12.08) Korean Patent Registration No. 10-0596507 (2006.06.27) Korean Registered Patent No. 10-0650135 (2006.11.20)

An object of the present invention is to provide a cement additive composition capable of increasing the grinding efficiency of cement while improving the compressive strength properties of mortar or concrete.

In order to solve the above problems, the present invention provides a cement additive composition comprising a compound of Formula 1 and a compound of Formula 2 below.

Formula 1

In Formula 1,

R ₁ , R ₂ and R ₃ independently of each other are hydrogen or hydroxy-(C ₁ -C ₆ )alkyl, except when R ₁ , R ₂ and R ₃ are all hydrogen;

Formula 2

In Formula 2,

R ₄ and R ₅ independently of each other are hydrogen or hydroxy-(C ₁ -C ₆ )alkyl;

R ₆ is hydroxy-(C ₁ -C ₆ )alkyl;

Z is (C ₁ -C ₆ )alkylene.

The present invention can prevent particle aggregation due to static electricity generated during the grinding process, improve the flowability of cement, increase grinding efficiency, and improve cement initial strength and late strength (long-term strength).

Since the present invention can apply various transformations and have various embodiments, specific embodiments will be illustrated in the drawings and described in detail in the detailed description. However, this is not intended to limit the present invention to specific embodiments, and should be understood to include all conversions, equivalents, or substitutes included in the spirit and scope of the present invention. In describing the present invention, if it is determined that a detailed description of related known technologies may obscure the gist of the present invention, the detailed description will be omitted.

The present invention provides a cement additive composition comprising a compound represented by Formula 1 below and a compound represented by Formula 2 below.

Formula 1

In Formula 1, R ₁ , R ₂ and R ₃ are each independently hydrogen or hydroxy-(C ₁ -C ₆ )alkyl, except when all of R ₁ , R ₂ and R ₃ are hydrogen,

Formula 2

In Formula 2, R ₄ and R ₅ are each independently hydrogen or hydroxy-(C ₁ -C ₆ )alkyl, R ₆ is hydroxy-(C ₁ -C ₆ )alkyl, and Z is (C1- C6) alkylene.

In one embodiment according to the present invention, R ₁ , R ₂ and R ₃ in Formula 1 are each independently hydroxy-(C ₁ -C ₃ )alkyl.

In one embodiment according to the present invention, in Formula 2, R ₄ , R ₅ and R ₆ are each independently hydroxy-(C ₁ -C ₃ )alkyl, and Z is (C ₁ -C ₃ )alkylene .

In one embodiment according to the present invention, in Formula 1 and Formula 2, R ₁ , R ₂ , R ₃ , R ₄ , R ₅ and R ₆ are hydroxy-(C ₁ -C ₃ )alkyl, and these 6 Substituents are all the same, and Z is (C ₁ -C ₃ )alkylene, which is the same as an alkylene group excluding hydroxy from R ₁ , R ₂ , R ₃ , R ₄ , R ₅ and R ₆ .

In one embodiment according to the present invention, in Formula 1, R ₁ , R ₂ and R ₃ are hydroxyethyl, and in Formula 2, R ₄ , R ₅ and R ₆ are hydroxyethyl, Z is an ethylene group (-CH ₂ CH ₂ -) or a propylene group (-CH ₂ CH ₂ CH ₂ -).

In the compound of Formula 2, a structure having an amine group, a hydrophilic -OH group, and an alkyl group in the molecule has an affinity for ionic particles generated by mechanical grinding of cement clinker and is adsorbed to remove surface energy to lower cohesive energy, Since there is no agglomeration, continuous grinding is possible and grinding efficiency is improved.

In one embodiment according to the present invention, the cement additive composition according to the present invention includes triethanolamine and diethanolamine glycol ether of the following formula (3).

Formula 3

The compound of Formula 3 is an ether compound containing a nonionic amine group and three OH groups showing hydrophilicity, and may exhibit affinity by adsorbing to ions generated by mechanical grinding or charged clinker elements. In addition, the alkyl group substituted with an amine group exhibits hydrophobicity, and the alkyl group maximizes the steric hindrance in the molecular structure so that the dispersed particles do not aggregate and at the same time acts as a lubricant, thereby reducing the grinding time per unit time and uniformly grinding the particle size. can play a role.

In the present invention, by preparing the compound of Formula 2 and using it together with an alcoholamine compound as a cement additive composition, aggregation of particles due to static electricity generated during grinding is prevented, and the flowability of cement is improved to increase grinding efficiency, cement strength can be improved.

The cement additive composition according to the present invention is characterized in that it can serve both as a cement grinding aid for improving grinding efficiency and as a cement functional grinding aid for enhancing the compressive strength of mortar/concrete.

The cement additive composition of the present invention is not limited to achieving the purpose of grinding cement clinker and expressing high strength, but, for example, 25 to 45% by weight of the compound of Formula 1 and 25 to 40% by weight of the compound of Formula 2 can include In another embodiment, 30 to 40% by weight of the compound of Formula 1 and 30 to 35% by weight of the compound of Formula 2 may be included. In another embodiment, 35 to 40% by weight of the compound of Formula 1 and 30 to 40% by weight of the compound of Formula 2 may be included.

The cement additive composition of the present invention is prepared by reacting the compound of Formula 1 and (C ₂ -C ₆ )alkylene oxide in a molar ratio of 1:1 to 1:5, for example, 1:1, in the presence of an anti-discoloration agent. It can be. The anti-discoloration agent may be at least one compound selected from the group consisting of hydrazine monohydrate, phosphorous acid, hypophosphorous acid, hydroxylamine, sodium borohydride, sodium hydrogen carbonate and sodium hydrogen sulfite, compared to the input amount of the compound of Formula 1 1,000-3,000 ppm or 1,500-2,000 ppm may be used.

In one embodiment of the present invention, as shown in Scheme 1 below, the cement additive composition contains triethanolamine and ethylene oxide in a molar ratio of 1:1 to 1:3, such as 1:1, in the presence of hydrazine monohydrate. It can be prepared by reacting with

Scheme 1

In another embodiment of the present invention, the cement additive composition is diethanolamine and ethylene oxide in a molar ratio of 1:2 to 1:4, such as 1:2, in the presence of hydrazine monohydrate, as shown in Scheme 2 below. It can be prepared by reacting in a molar ratio of

Scheme 2

In another embodiment of the present invention, the cement additive composition is prepared by combining monoethanolamine and ethylene oxide in a molar ratio of 1:3 to 1:5, such as 1:3, in the presence of hydrazine monohydrate, as shown in Scheme 3 below. It can be prepared by reacting in a molar ratio of

Scheme 3

In order to achieve grinding efficiency, the cement additive composition according to the present invention is preferably added in an amount of 0.02-0.2 parts by weight based on 100 parts by weight of cement clinker, but is not limited to the above range.

The cement additive composition according to the present invention may be added before, during or after grinding the cement clinker.

Hereinafter, embodiments of the present invention will be described in detail so that those skilled in the art can easily implement the present invention. However, the present invention may be embodied in many different forms and is not limited to the embodiments set forth herein.

Example

Synthesis Example : Preparation of cement additive composition according to the present invention

300 g of TEA was put into an autoclave-type high-pressure reactor (1.5 L), and 0.48 g of hydrazine monohydrate was added at a concentration of 1,600 ppm compared to TEA. After tightening the lid of the reactor, nitrogen substitution was performed 5 times while stirring, and the temperature of the reactor was raised to 100°C. When the temperature reached 100 ° C, 88 g of EO (ethylene oxide) was slowly injected, and the reaction was allowed to react for 2 hours within a reaction pressure of 5 bar while preventing the reaction temperature from exceeding 120 ° C. It was confirmed that the composition obtained therefrom contained 35.6% by weight of TEA, 39.1% by weight of DEAGE and 25.3% by weight of other heaviers based on the total weight.

test example

1) Residue rate (%) measurement

In accordance with KS L 5112, which is a test method for cement fineness using a standard sieve of 45 μm, the cement fineness was evaluated by measuring the ratio of residues that did not pass the standard sieve (residual percentage).

2) Mortar test

In accordance with KS L ISO 679, the compressive strength of cement was measured on the basis of 1 day, 3 days, 7 days and 28 days.

3) Fineness (㎠/g)

It was measured according to KS L 5106, which is a test method for the powderiness of Portland cement by an air permeation device.

<Test Example 1> Cement grinding: using the composition of Synthesis Example as a cement additive

- 1.35 g of water was added to 1,425 g (95%) of cement clinker and 75 g (5%) of gypsum, 0.45 g (0.03%) of the composition of the Synthesis Example was mixed, and pulverized with a ball mill made of steel for 36 minutes, The results of measuring physical properties by the above method are shown in Table 1.

<Comparative Test Example 1-1> Cement grinding: using diethanol isopropanol amine as a cement additive

- Cement grinding was performed in the same manner as in Test Example 1, except that 0.45 g (0.03%) of diethanol isopropanol amine was mixed instead of 0.45 g (0.03%) of the composition of Synthesis Example. Table 1 shows.

<Comparative Test Example 1-2> Cement grinding: using a compound of formula 4 and diethylene glycol as cement additives

- Instead of 0.45g (0.03%) of the composition of Synthesis Example, a mixture of the compound of Formula 4 and diethylene glycol (mixing weight ratio of the compound of Formula 4: diethylene glycol = 1: 1) 0.45g (0.03%) was added Cement grinding was performed in the same manner as in Test Example 1 except for the above, and the results of measuring physical properties by the above method are shown in Table 1.

formula 4

<Comparative Test Example 1-3> Cement grinding: using a compound of formula 5 and diethylene glycol as cement additives

- Instead of 0.45g (0.03%) of the composition of Synthesis Example, a mixture of the compound of Formula 5 and diethylene glycol (mixing weight ratio of the compound of Formula 5: diethylene glycol = 1: 1) 0.45g (0.03%) was added Cement grinding was performed in the same manner as in Test Example 1 except for the above, and the results of measuring physical properties by the above method are shown in Table 1.

Formula 5

<Test Example 2> Mortar test

- 1,350 g of sand and 225 g of water (water/cement 50%) were added to 450 g of the cement prepared in Test Example 1 and mixed, and the compressive strength properties were measured in accordance with KS L ISO 679. To measure the compressive strength, mortar specimens were first prepared. Specifically, sand was gradually added while mixing for 30 seconds at a first speed (rotation speed 140 ± 5 rpm, revolution speed 62 ± 5 rpm) by starting the mixer after putting water in the mixing container and cement. The mixer was stopped and mixed again for 30 seconds by changing to the second speed (285 ± 10 rpm rotation speed, 125 ± 10 rpm revolution speed). The mixer was stopped and the mortar was allowed to stand for 90 seconds. At this time, for the first 15 seconds, the mortar attached to the side of the container was scraped with a scraper, and the container was covered with a lid for the remaining time. Mixing was continued for 1 minute at the second speed and then stopped. When remixing was required, the mortar adhering to the container was scraped off with a scraper. The results are shown in Table 2.

<Comparative Test Example 2-1> Mortar test

- 1,350 g of sand and 225 g of water (water/cement 50%) were added to 450 g of cement prepared in Comparative Test Example 1-1, and the compressive strength properties were measured in accordance with KS L ISO 679. The results are shown in Table 2.

<Comparative Test Example 2-2> Mortar test

- 1,350 g of sand and 225 g of water (water/cement 50%) were added to 450 g of the cement prepared in Comparative Test Example 1-2, and the compressive strength properties were measured in accordance with KS L ISO 679. The results are shown in Table 2.

<Comparative Test Example 2-3> Mortar test

- 1,350 g of sand and 225 g of water (water/cement 50%) were added to 450 g of cement prepared in Comparative Test Example 1-3, and the compressive strength properties were measured according to KS L ISO 679. The results are shown in Table 2.

Prescription rate (%) Grinding time (min) Fineness (cm ² /g) Residue (%) Test Example 1 0.03 36 3,430 3.91 Comparative Test Example 1-1 0.03 36 3,400 4.03 Comparative test example 1-2 0.03 36 3,200 12.0 Comparative test example 1-3 0.03 36 3,050 12.2

1 day (MPa) 3 days (MPa) 7 days (MPa) 28 days (MPa) Test Example 2 18.54 31.88 47.27 57.8 Comparative test example 2-1 17.21 30.20 46.14 57.1 Comparative test example 2-2 6.46 24.56 32.18 44.80 Comparative test example 2-3 6.98 25.32 33.56 45.60

The effect of grinding efficiency can be confirmed by the powder value, and the grinding efficiency is about 2,300 cm ² /g. As shown in Table 1, the powder size using diethanol isopropanol amine as a cement additive is 3,400 cm ² / g (Comparative Test Example 1-1), and in the case of Comparative Test Examples 1-2 and 1-3, the powder fineness was 3,200 cm ² /g and 3,050 cm ² /g, respectively, according to the present invention described in Synthesis Example The fineness of cement using the composition according to the present invention as a grinding aid was 3,430 cm ² /g (Test Example 1), and Comparative Test Examples 1-1, 1-2 and 1-3, and Test Example 1 according to the present invention were all pulverized. It was confirmed that the performance was excellent. On the other hand, in the residue ratio, Comparative Test Example 1-1 showed 4.03%, Comparative Test Example 1-2 showed 12.0%, Comparative Test Example 1-3 showed 12.2%, and Synthesis Example showed 3.91% As shown, it was confirmed that the residue rate of Test Example 1 according to the present invention was the best. As such, it could be confirmed that the composition according to the present invention showed an increase in powder degree and a decrease in residue rate compared to Comparative Test Examples 1-1, 1-2 and 1-3.

Table 2 shows the compressive strength properties used as a cement functional grinding aid, and the initial strength is determined by 3 or 7 day data, and the late strength is determined by 28 day data. Looking at the results shown in Table 2, Test Example 2 corresponding to the present invention has an initial strength (7 days) of about 1 MPa and a late strength (28 days) of about 0.7 MPa more compressive strength than Comparative Test Example 2-1, and , Compared to Comparative Test Examples 2-2 and 2-3, it was confirmed that the initial strength (7 days) and late strength (28 days) were significantly superior to 10 MPa or more.

As above, specific parts of the present invention have been described in detail, and for those skilled in the art, it is clear that these specific descriptions are only preferred embodiments, and the scope of the present invention is not limited thereby. something to do. Accordingly, the substantial scope of the present invention will be defined by the appended claims and their equivalents.

Claims (10)

A cement additive composition comprising a compound of Formula 1 and a compound of Formula 2 below,
The content of the compound of Formula 1 is 25 to 45% by weight based on the weight of the total composition, and the content of the compound of Formula 2 is 25 to 40% by weight based on the weight of the total composition, cement additive composition:
Formula 1

In Formula 1,
R ₁ , R ₂ and R ₃ independently of each other are hydrogen or hydroxy-(C ₁ -C ₆ )alkyl, except when R ₁ , R ₂ and R ₃ are all hydrogen;
Formula 2

In Formula 2,
R ₄ and R ₅ independently of each other are hydrogen or hydroxy-(C ₁ -C ₆ )alkyl;
R ₆ is hydroxy-(C ₁ -C ₆ )alkyl;
Z is (C ₁ -C ₆ )alkylene. The cement additive composition according to claim 1, wherein R ₁ , R ₂ and R ₃ in Formula 1 are each independently hydroxy-(C ₁ -C ₃ )alkyl. The cement additive according to claim 1, wherein in Formula 2, R ₄ , R ₅ and R ₆ are each independently hydroxy-(C ₁ -C ₃ )alkyl, and Z is (C ₁ -C ₃ )alkylene. composition. The cement additive composition according to claim 1, wherein the compound of Formula 1 is triethanolamine and the compound of Formula 2 is diethanolamine glycol ether. delete Preparation of the cement additive composition according to any one of claims 1 to 5, comprising reacting the compound of Formula 1 and (C ₂ -C ₆ )alkylene oxide in a molar ratio of 1:1 to 1:5. Way. The method of claim 6, wherein the compound of Formula 1 is triethanolamine and the (C ₂ -C ₆ )alkylene oxide is ethylene oxide. The method of claim 6, wherein the step is performed in the presence of at least one anti-discoloration agent selected from the group consisting of hydrazine monohydrate, phosphorous acid, hypophosphorous acid, hydroxylamine, sodium borohydride, sodium hydrogen carbonate and sodium hydrogen sulfite, The method of producing a cement additive composition, wherein the anti-discoloration agent is used in an amount of 1,000-3,000 ppm relative to the input amount of the compound of Formula 1. A cement composition comprising 0.02-0.2 parts by weight of the cement additive composition according to any one of claims 1 to 5, based on 100 parts by weight of cement clinker. The cement composition according to claim 9, wherein the cement additive composition is added before, during or after grinding of the cement clinker.