KR101335033B1 - High performance grinding aid for minuteness shatter of mineral contain Cement composition - Google Patents

Abstract

The present invention relates to a cement composition comprising a high functional grinding aid. More specifically, by mixing a compound having a amine group and a hydroxyl group in one compound and imparting hydrophilicity and hydrophobicity to the terminal of the compound structure and including it as a high functional grinding aid, the existing two to three compounds are mixed. It relates to a cement composition that can be included as a high-functional grinding aid as a compound different from that used.

Description

High performance grinding aid for mineral grinding, and cement composition comprising same {High performance grinding aid for minuteness shatter of mineral contain Cement composition}

The present invention relates to a cement composition comprising a high functional grinding aid for mineral grinding. More specifically, the present invention relates to a cement composition including both an amine group and a hydroxyl group in one compound and an organic compound imparted with hydrophilicity and hydrophobicity at the terminal of the compound structure as a grinding aid.

In general, the typical mineral industry is the cement industry. As raw materials used in cement production, coke, sludge, dust, and the like are used as raw materials for limestone, silica, clay, iron ore, slag, or mixtures thereof. When the mixture is finely pulverized and treated at 1,450 ° C. in the kiln, the limestone component in the raw material is combined with silica, alumina and iron to form a clinker mineral. When these minerals react with water, they harden. These are called cement clinker, and the clinker is produced as a final product cement through mixed grinding process like gypsum.

In the cement manufacturing process, grinding is a very important process that determines the final performance as a product. The purpose of the grinding is to increase the surface area of the cement clinker to increase the reactivity and make the particulate particles easily, as well as to grind the rocks to take useful ingredients and increase the mixing effect. Grinding Aid.

Commonly used grinding aids include amine acetate, which is a single compound, and monoethylene glycol (MEG) and diethylene glycol (DEG) as ethylene glycol. Alcohols include propylene glycol, and glycol alkanolamines include triethanol amine (TEA).

As a technique for the grinding aid of minerals, the technology related to the "pulverization method of minerals using waste antifreeze (Korea Patent No. 0222776)", and the mixing ratio for the two-component or three-component system used as the grinding aid as a variable In the case of using the preparation, there is a "mineral grinding milling aid (Korean Patent No. 0650175)".

As described above, the prior art has led to an increase in crushing efficiency and productivity improvement when crushing cement clinker with a single compound or two-component and three-component mixtures.

Although some advances have been made in increasing the grinding efficiency and productivity of the clinker as described above, in recent years, due to the development of powder engineering and the demand for quality, in addition to the effects of existing concepts such as an increase in mill efficiency, Research on grinding aids that improve flow characteristics and compressive strength is continuing.

Republic of Korea Patent No. 0222776 (July 7, 1999) Republic of Korea Patent No. 0650175 (November 20, 2006)

The present invention is to meet the above requirements, by including a compound containing both an amine group and a hydroxy group in one compound and imparted hydrophilicity and hydrophobic properties to the terminal of the compound structure as a high-functional grinding aid, The purpose of the present invention is to provide high quality cement which improves the hydration, fluidity and compressive strength and workability.

 In order to achieve the above object, the present invention synthesizes a compound which includes both an amine group and a hydroxyl group in one compound and imparts hydrophilicity and hydrophobic property to the terminal of the compound structure, and is used as a high-functional grinding aid. It relates to a cement composition that can be used alone as a grinding aid. More specifically, the present invention by using the organic compound as a high-functional grinding aid, to increase the grinding efficiency by preventing the stability of heat generated in the mill and coating of the ball, improve the hydration, fluidity, compressive strength of the cement and The present invention relates to a cement composition capable of improving workability.

The high functional grinding aid includes the following Chemical Formulas 1 to 3.

[Formula 1]

(2)

(3)

In Formulas 1 to 3, A ₁ , A ₂ , B ₁ , B ₂ , C _1, and C ₂ are each independently,

,

,

,

,

,

,

,

,

,

,

및 하이드록시기에서 선택되고, 또한 상기 R₁ 내지 R₉는 각각 독립적으로,

,

,

,

,

및 하이드록시기에서 선택되며, 상기 R₁₁ 내지 R₁₂는 각각 독립적으로,

,

And a hydroxy group, wherein R ₁ to R ₉ are each independently,

,

,

,

,

And it is selected from a hydroxyl group, wherein R ₁₁ to R ₁₂ are each independently,

,

,

및 하이드록시기에서 선택된다. 단, 상기 A₁ 및 A₂, B₁ 및 B₂, C₁ 및 C₂, R₁내지 R₉, R₁₁ 내지 R₁₂는 동시에 하이드록시기를 갖을 수 없다.

,

And hydroxy groups. However, A ₁ and A ₂ , B ₁ and B ₂ , C ₁ and C ₂ , R ₁ to R ₉ , and R ₁₁ to R ₁₂ may not have a hydroxyl group at the same time.

Hereinafter, each configuration will be described in detail.

The present invention synthesizes a compound containing an amine group and a hydroxyl group in one compound and imparting hydrophobicity and hydrophilic property to the terminal of the compound structure and using the mixture as a highly functional grinding aid. It relates to a cement composition which can be used as a grinding aid only one compound different from that used. More specifically, one compound includes an amine group and a hydroxyl group, and both hydrophilic and hydrophobic properties are included at the terminal of the compound structure, and thus, conventional DEG (diethylene glycol), TEA (triethanolamine), TIPA (triisopropanolamine), and the like are included. It relates to a cement composition comprising a high functional grinding aid that can compensate for the complexity of the process due to the mixing of materials, layer separation and mutual coagulation due to specific gravity difference.

The high functional grinding aid may be used 0.001 ~ 0.5 wt% when manufacturing cement. If the content of the high functional grinding aid in the cement production is less than 0.001 wt%, it can not fully exhibit the effect of promoting the grinding, if it exceeds 0.5wt% no further grinding promoting effect does not appear and does not have a significant effect on the economic efficiency Not desirable

The high functional grinding aid includes the following formula (1).

[Formula 1]

,

,

,

,

,

및 하이드록시기에서 선택되고, 또한 상기 R₁ 내지 R₉는 각각 독립적으로,

,

,

,

,

및 하이드록시기에서 선택되며, 상기 R₁₁ 내지 R₁₂는 각각 독립적으로,

,In Formula 1, A ₁ and A ₂ are each independently,

,

,

,

,

,

And a hydroxy group, wherein R ₁ to R ₉ are each independently,

,

,

,

,

And it is selected from a hydroxyl group, wherein R ₁₁ to R ₁₂ are each independently,

,

,

및 하이드록시기에서 선택된다. 단, 상기 A₁ 내지 A₂, R₁ 내지 R₉, R₁₁ 내지 R₁₂는 동시에 하이드록시기를 갖을 수 없다.

,

And hydroxy groups. Provided that A ₁ to A ₂ and R ₁ To R ₉ , R ₁₁ to R ₁₂ may not have a hydroxyl group at the same time.

 In addition, the compound of Chemical Formula 1 may include the following Chemical Formula 4.

[Chemical Formula 4]

The high functional grinding aid includes the following formula (2).

(2)

,

,

,

,

,

및 하이드록시기에서 선택되고, 또한 상기 R₁ 내지 R₉는 각각 독립적으로,

,

,

,

,

및 하이드록시기에서 선택되며, 상기 R₁₁ 내지 R₁₂는 각각 독립적으로,

,

,

및 하이드록시기에서 선택된다. 단, 상기 B₁ 내지 B₂, R₁ 내지 R₉, R₁₁ 내지 R₁₂는 동시에 하이드록시기를 갖을 수 없다.In Formula 2, B ₁ and B ₂ are each independently,

,

,

,

,

,

And a hydroxy group, wherein R ₁ to R ₉ are each independently,

,

,

,

,

And it is selected from a hydroxyl group, wherein R ₁₁ to R ₁₂ are each independently,

,

,

And hydroxy groups. However, the B ₁ to B ₂ , R ₁ to R ₉ , R ₁₁ to R ₁₂ may not have a hydroxyl group at the same time.

In addition, Formula 2 may include the following Formula 5.

[Chemical Formula 5]

The high functional grinding aid includes the following formula (3).

(3)

,

,

,

,

,

및 하이드록시기에서 선택되고, 또한 상기 R₁ 내지 R₉는 각각 독립적으로,

,

,

,

,

및 하이드록시기에서 선택되며, 상기 R₁₁ 내지 R₁₂는 각각 독립적으로,

,

,

및 하이드록시기에서 선택된다. 단, 상기 C₁ 내지 C₂, R₁ 내지 R₉, R₁₁ 내지 R₁₂는 동시에 하이드록시기를 갖을 수 없다.In Formula 3, C ₁ and C ₂ are each independently,

,

,

,

,

,

And a hydroxy group, wherein R ₁ to R ₉ are each independently,

,

,

,

,

And it is selected from a hydroxyl group, wherein R ₁₁ to R ₁₂ are each independently,

,

,

And hydroxy groups. However, the C ₁ to C ₂ , R ₁ To R ₉ , R ₁₁ to R ₁₂ may not have a hydroxyl group at the same time.

Formula 3 may include the following Formula 6.

[Chemical Formula 6]

Urea (urea), melamine (melamine, 2, 4,6-triamino-1,3,5-triazine), ethylene diamine (ethylene diamine), amino alcohol (sec-amino alcohol) , Ethanolamine (mono, di-ethanol amine), sulfanilic acid (sulfanilic acid), sulfamic acid (sulfamic acid), sulfanilamide (sulfanilamide), ethanolamines (mono, di, tri-ethanol amine), glycerine (glycerine ) Can be used.

,

및

에서 선택되는 하나 또는 두 개의 치환기를 가질 수 있다. 상기와 같은 말단 구조를 위하여 아세트산(acetic acid), 개미산(formic acid) 및 아세트산무수물(acetic anhydride)등에서 선택되는 하나 또는 두 개 이상을 사용 하여 상기 화합물을 합성 할 수 있다.In addition, in order to give both hydrophilicity and hydrophobicity to the terminal of the compound, the terminal structure of the compound,

,

And

It may have one or two substituents selected from. For the terminal structure as described above, the compound may be synthesized using one or more selected from acetic acid, formic acid, acetic anhydride, and the like.

By imparting properties of hydrophilicity and hydrophobicity to the terminal of the compound structure, the dispersibility and affinity for water is high, the grinding efficiency during clinker grinding is high, the production efficiency per hour is high, and energy is saved. In addition, the cement thus prepared is coated on the surface of the cement to increase the strength with a high water-resisting effect during mortar work, and at the same time improve the fluidity by lowering the viscosity to improve workability.

In the present invention, the high-functional grinding aid is present in the amine group, the stable coordination to the cation of the non-covalent electron pair in the amine group induces the dispersion stability between the particles according to the uniform repulsion between the cement particles to improve the workability of the cement concrete and compression Physical properties such as strength can be improved.

In addition, since the high functional grinding aid is a hydroxyl group, it improves productivity by preventing coating of the ball inside the mill during the cement clinker grinding process and increases the diffusion coefficient of the organic compound to the clinker to produce uniform particles. To enable the manufacture of cement.

The high-functional grinding aid can improve the hydration and fluidity of the cement by being properly hydrophilic and hydrophobic in the compound structure.

In the cement composition comprising a compound having an amine group and a hydroxyl group in the structure of the high-functional grinding aid according to the present invention, the compound imparted hydrophilicity and hydrophobic properties to the terminal of the structure as a high-functional grinding aid, It is more economical than the grinding aid having the above effects by mixing the compound. More specifically, the flowability and hydrability of the cement are further improved, and when the cement clinker is pulverized, energy is reduced on the surface of the particles to increase the pulverization efficiency, thereby preparing high active fine particles to improve compressive strength.

Hereinafter, the present invention will be described by way of example in order to describe the present invention in more detail, but the present invention is not limited to the following examples.

Example 1

600 mg 1,3-bis (hydroxymethyl) urea (600 mg) and diethanolamine in a 2500 mL five-neck round flask equipped with thermometer, condenser, distillation receiver and pH meter. diethanol amin) 1051 mg was added and stirred at a speed of 250 rpm using a mechanical stirrer, and 50 mg of sulfanilic acid was added as an acid catalyst, and the temperature was gradually raised to react at 80 ° C. for 3 hours to synthesize a light brown intermediate compound.

In the synthesized intermediate compound, 0.05 wt% of the acid catalyst p-toluenesulphonic acid was added to the monomer, and then 600 mg of acetic acid was gradually added thereto. The reaction temperature was increased to 120 ° C. and the reflux reaction was carried out for 3 hours. After 4 hours of dehydration at 140 ° C., the reaction was carried out to an acid value of 30 mg KOH / g, yielding 96 when the reaction was terminated when the viscosity was 25 cP (Brookfield viscometer DV II, spinder # 3). A dark brown compound of formula 1 was obtained.

Scheme of the synthesized compound of Formula 1 is shown in Scheme 1 below.

[Reaction Scheme 1]

[Example 2]

 751 mg of 1- (hydroxymethylamino) propan-2-ol and 921 mg of glycerin in a 2500 mL five-neck round flask equipped with thermometer, condenser, distillation receiver and pH meter After adding 50mg of sulfanilic acid as an acid catalyst while stirring at a speed of 250rpm using a mechanical stirrer, the temperature was gradually raised and reacted at 80 ° C for 3 hours to synthesize a pale yellow intermediate compound.

After adding 0.05 wt% of the acid catalyst p-toluenesulfonic acid as a monomer to the synthesized intermediate compound, gradually adding 600 mg of acetic acid, raising the reaction temperature to 120 ° C. and performing reflux reaction for 3 hours, and again at 130 ° C. for 4 hours. After 4 hours of dehydration at 140 ° C., the acid value was reacted to 30 mg KOH / g, and the yield was 93% while terminating the reaction when the viscosity was 20 cP (Brookfield viscometer DV Ⅱ, spinder # 3). Phosphorus dark brown compound of formula (2) was obtained.

The reaction scheme of the synthesized compound of Formula 2 is shown in Scheme 2 below.

 [Reaction Scheme 2]

  [Example 3]

In a 2500 mL five-neck round flask equipped with thermometer, condenser, distillation receiver and pH meter, 601 mg of (2- (hydroxymethylamino) ethylamino) methanol) 581 mg of propylene oxide was added. Stirring at a speed of 250rpm using a mechanical stirrer while slowly adding, 50mg of sulfanilic acid was added as an acid catalyst, gradually increasing the temperature and reacting at 40 ° C for 5 hours to synthesize a pale yellow intermediate compound.

After adding 0.05 wt% of the acid catalyst p-toluenesulphonic acid as a monomer to the synthesized intermediate compound, gradually adding 600 parts of acetic acid, raising the reaction temperature to 120 ° C. and performing reflux reaction for 3 hours, and again at 130 ° C. for 4 hours. After 4 hours of dehydration at 140 ° C., the reaction was carried out to an acid value of 30 mg KOH / g. The yield was 91% while terminating the reaction when the viscosity was 50 cP (Brookfield viscometer DV Ⅱ, spinder # 3). A light brown compound of formula 3 was obtained.

The reaction scheme of the synthesized compound of Formula 3 is shown in Scheme 3 below.

 Scheme 3

 [Experimental Example 1]

50:50 mixture of high functional grinding aid (GA-1 ~ 3) which is a synthesized compound of the present invention and DEG alone (Plain-1), which is a conventional grinding aid, and triethanol amine (TEA) having DEG and an amine group (Plain- 2) and DEG and triisopropylamine (TIPA) having an amine group and a hydroxyl group in the monomer structure were mixed (Plain-3) at a ratio of 50:50 and added during the clinker grinding to measure the grinding efficiency. The amount of the grinding aid was 0.02 wt% compared to the clinker, and the powder level was measured after the first grinding for 25 minutes, and the final powder level was measured with the extraction time of 5 minutes. Powder level was measured according to KS L 5106.

The water / cement ratio of the cement paste was tested at (30: 100) condensation time measurement at 30% and the mini slump at 45%.

The compressive strength of mortar was cement: standard yarn: water ratio of 1: 2.45: 0.48, and a mold was prepared to measure the compressive strength for 3, 7, 28 days.

  [Experimental Example 2]

The concrete test on the prepared cement is designed according to the standard concrete specification (25-24-150) (KS F 4009) and high strength concrete (25-40-600) (KS F 4009) as shown in Table 3 The compressive strength was measured for ages 3, 7, and 28 days.

Table 1. Grinding performance test result

Table 2: Settling Time of Prepared Cement, Minislump and Mortar Compressive Strength of Paste

[Experimental Example 3]

Concrete application test of prepared cement

Table 3: Concrete Specification

Table 4: Concrete Test Results

Claims (11)

Grinding aid for grinding the mineral represented by the formula (1).
[Chemical Formula 1]

In Formula 1, A ₁ and A ₂ are each independently,

,

,

,

,

,

And hydroxy group,
In addition, R ₁ to R ₉ are each independently,

,

,

,

,

And hydroxy groups,
R ₁₁ to R ₁₂ are each independently,

,

,

And hydroxy groups. However, A ₁ to A ₂ may not have a hydroxy group at the same time, the formula (1) excludes a combination that does not include at least one hydroxy group and at least one amine group. The grinding aid for grinding minerals according to claim 1, wherein the compound of Chemical Formula 1 comprises the following Chemical Formula 4.
[Chemical Formula 4]

The grinding aid for mineral grinding according to claim 2, wherein the compound of Formula 4 comprises the following compound (1-19).

Grinding aid for grinding the mineral represented by the formula (2).
(2)

In Formula 2, B ₁ and B ₂ are each independently,

,

,

And it is selected from a hydroxyl group, and wherein R _{One To} R _{5 Are} each independently,

,

And hydroxy groups. However, B ₁ to B ₂ may not have a hydroxyl group at the same time, the formula (2) excludes a combination that does not include at least one hydroxy group and at least one amine group. The method of claim 4. Compound of Formula 2 is a grinding aid for grinding minerals comprising the following formula (5).
[Chemical Formula 5]

The grinding aid for grinding minerals according to claim 5, wherein the compound of formula 5 comprises the following compound (2-13).

Grinding aid for mineral grinding comprising an amine group and a hydroxyl group represented by the formula (3).
(3)

In Formula 3, C ₁ and C ₂ are each independently,

,

,

And it is selected from a hydroxyl group, and wherein R _{One To} R _{5 Are} each independently,

,

And hydroxy groups. However, C ₁ to C ₂ may not have a hydroxy group at the same time, the formula (3) excludes a combination that does not include at least one hydroxy group and at least one amine group. The grinding aid for the grinding of minerals according to claim 7, wherein the compound of Chemical Formula 3 comprises the following Chemical Formula 6.
[Chemical Formula 6]

The grinding aid for grinding minerals according to claim 8, wherein the compound of Chemical Formula 6 includes the following compound (3-1).

A cement composition comprising a grinding aid for grinding minerals according to any one of claims 1 to 9. The cement composition of claim 10, wherein the mineral grinding aid is included in an amount of 0.001 to 0.5 wt%.