KR101853124B1 - Cement admixture composition and method for preparing the same - Google Patents

Abstract

The present invention relates to an unsaturated polyalkylene glycol ether-based monomer represented by the following formula (1): An unsaturated carboxylic acid monomer represented by the following formula (2); And a carboxylic acid-based copolymer polymerized from an acrylate-based monomer, and a reactive surfactant, and a method for producing the same.
[Chemical Formula 1]
C _m H _2m-1 O (C _n H _2n O) _k (R ¹ O) ₁ R ²
(2)

Description

TECHNICAL FIELD The present invention relates to a cement admixture composition and a method for producing the same,

The present invention relates to a cement admixture composition, and more particularly, to a cement admixture composition which is excellent in flowability and slump retention ability as compared with a conventional cement admixture composition and can exhibit sufficient copolymerization, And a method for producing the same.

Cement admixture is widely used in cement compositions such as cement paste, mortar, and concrete. When the cement admixture is used, it is possible to increase the fluidity of the cement composition and reduce the water content of the cement composition, thereby improving the strength and durability of the cured product.

Conventionally, a cement admixture such as lignin type or naphthalene sulfonic acid type has been used, but recently, a cement admixture containing a polycarboxylic acid type copolymer as a cement admixture has been proposed. A cement admixture containing a polycarboxylic acid-based copolymer as a main component can exhibit high water reducing performance. As the polycarboxylic acid-based copolymer, a polycarboxylic acid-based copolymer containing a structural unit derived from an unsaturated polyalkylene glycol ether monomer and a structural unit derived from an unsaturated carboxylic acid monomer is known. However, the unsaturated polyalkylene glycol ether-based monomer has a problem of low copolymerization as compared with the ester-based monomer. Therefore, a polycarboxylic acid-based copolymer containing a structural unit derived from an unsaturated polyalkylene glycol ether-based monomer and a structural unit derived from an unsaturated carboxylic acid-based monomer can not be obtained at all in a polycarboxylic acid-based copolymer having a desired copolymerization ratio , Even if obtained, the ratio of the polymer is lowered, and the quality of the polymer is deteriorated, and the manufacturing cost is increased. Further, when a polycarboxylic acid-based copolymer containing a structural unit derived from an unsaturated polyalkylene glycol ether monomer and a structural unit derived from an unsaturated carboxylic acid monomer is used as a cement admixture, it is difficult to obtain a sufficient cement admixture And when it is produced by a copolymerization method known so far, sufficient copolymerization of the unsaturated polyalkylene glycol ether monomer is not easily manifested.

Therefore, when a polycarboxylic acid-based copolymer containing a structural unit derived from an unsaturated polyalkylene glycol ether monomer and a structural unit derived from an unsaturated carboxylic acid monomer is produced, sufficient copolymerization is performed with respect to the unsaturated polyalkylene glycol ether monomer There is a growing demand for a technique that can be easily expressed.

The present invention relates to a cement admixture composition to which a conventional cement admixture is applied is excellent in contrast, fluidity, and slump retention, has excellent slump retention performance over time, and also exhibits sufficient copolymerization of the composition, Improving cement admixture composition and a process for producing the same.

In the present specification, an unsaturated polyalkylene glycol ether-based monomer represented by the following formula (1); An unsaturated carboxylic acid monomer represented by the following formula (2); And a carboxylic acid-based copolymer polymerized from an acrylate-based monomer, and a reactive surfactant.

[Chemical Formula 1]

C _m H _2m-1 O (C _n H _2n O) _k (R ¹ O) ₁ R ²

(2)

In formula (1), R ¹ O is one or more oxyalkylene groups having 2 to 10 carbon atoms, R ² is hydrogen or an alkyl group having 1 to 20 carbon atoms,

m is from 2 to 4, n is from 3 to 6, k is 0 or 1, 1 is an average addition molar number of oxyalkylene groups of 1 to 1,000,

In Formula (2), R ³ to R ⁵ are each independently hydrogen, an alkyl group having 1 to 10 carbon atoms, a sulfone group, a carboxyl group, or a combination thereof, M is hydrogen, a monovalent metal, a divalent metal, Or an organic amine group.

Further, the present invention provides a method for producing the above cement admixture composition.

Hereinafter, a cement admixture composition according to a specific embodiment of the present invention and a method for producing the same will be described in detail.

According to one embodiment of the present invention, an unsaturated polyalkylene glycol ether-based monomer represented by the following general formula (1); An unsaturated carboxylic acid monomer represented by the following formula (2); And a carboxylic acid-based copolymer polymerized from an acrylate-based monomer, and a curing agent composition containing a reactive surfactant can be provided.

[Chemical Formula 1]

C _m H _2m-1 O (C _n H _2n O) _k (R ¹ O) ₁ R ²

(2)

In formula (1), R ¹ O is one or more oxyalkylene groups having 2 to 10 carbon atoms, R ² is hydrogen or an alkyl group having 1 to 20 carbon atoms,

m is from 2 to 4, n is from 3 to 6, k is 0 or 1, 1 is an average addition molar number of oxyalkylene groups of 1 to 1,000,

In Formula (2), R ³ to R ⁵ are each independently hydrogen, an alkyl group having 1 to 10 carbon atoms, a sulfone group, a carboxyl group, or a combination thereof, M is hydrogen, a monovalent metal, a divalent metal, Or an organic amine group.

Hereinafter, the present invention will be described in detail.

The present inventors have found that an unsaturated polyalkylene glycol ether-based monomer represented by the above formula (1); An unsaturated carboxylic acid monomer represented by Formula 2; And a cement admixture composition prepared by adding a reactive surfactant to a carboxylic acid-based copolymer polymerized from an acrylate-based monomer have excellent fluidity and slump retention ability as compared with the conventional cement admixture composition, And that the composition shows satisfactory copolymerization, but the production time is shortened to improve the productivity. Based on this finding, the present invention has been completed.

The carboxylic acid-based copolymer according to one embodiment may be polymerized from unsaturated polyalkylene glycol ether-based monomer, unsaturated carboxylic acid-based monomer, and acrylate-based monomer.

The unsaturated polyalkylene glycol ether monomer may be a compound represented by the following Formula 1:

[Chemical Formula 1]

C _m H _2m-1 O (C _n H _2n O) _k (R ¹ O) ₁ R ²

In formula (1), R ¹ O is one or more oxyalkylene groups having 2 to 10 carbon atoms, R ² is hydrogen or an alkyl group having 1 to 20 carbon atoms,

m is 2 to 4, n is 3 to 6, k is 0 or 1,

l is an average addition mole number of oxyalkylene group added is 1 to 1,000.

For example, the unsaturated polyalkylene glycol ether monomer represented by the general formula (1) may include at least one of polyethylene glycol vinyl ether, polypropylene glycol vinyl ether, and polybutylene glycol vinyl ether. In one embodiment, for example, It is more preferable to use polybutylene glycol vinyl ether.

The monomer represented by the formula (1) preferably has an average addition mole number of oxyalkylene groups of 1 to 1,000. When the average addition mole number of the oxyalkylene group is 1 to 1,000, there is an effect of relatively improving the initial fluidity.

The unsaturated polyalkylene glycol ether monomer having unsaturated alkylene glycol ether as a raw material in the cement admixture composition according to one embodiment is a substance in which an ether group is present in the raw material like the compound of the above formula 1, It is possible to shorten the polymerization time of the cement admixture by 50% or more compared to the conventional product.

The unsaturated carboxylic acid-based monomer may be a compound represented by the following Formula 2:

(2)

In Formula (2), R ³ to R ⁵ are each independently hydrogen, an alkyl group having 1 to 10 carbon atoms, a sulfone group, a carboxyl group, or a combination thereof, M is hydrogen, a monovalent metal, a divalent metal, Or an organic amine group.

For example, the unsaturated carboxylic acid monomer represented by the general formula (2) may be at least one selected from the group consisting of acrylic acid, methacrylic acid, maleic acid, maleic anhydride, crotonic acid, citraconic acid, citraconic anhydride, itaconic anhydride, For example, in one embodiment, it is more preferable to use acrylic acid.

The acrylate monomer according to one embodiment may include a hydroxyl group, a carboxyl group or a salt thereof, and examples thereof include 2-hydroxyethyl methacrylate (2-hydroxyethyl methacrylate) as the (meth) 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, pentaerythritol triacrylate, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, etc. But is not limited thereto.

The acrylate monomer has a side chain higher than that of the unsaturated carboxylic acid monomer, thereby increasing the steric hindrance effect. Therefore, the repulsion between the monomers increases the fluidity and retention of the cement composition.

In addition, the cement admixture composition according to one embodiment further comprises a reactive surfactant. The reactive surfactant may be, but is not limited to, acetylenic surfactants such as acetylene glycol, ethoxylated acetylene glycol, acetyleneglycol combined with alkylphenyl, and the like.

The reactive surfactant contained in the cement admixture composition has a hydrophilic group at the terminal end thereof so that the bonding force with the cement particles can be enhanced and the dispersibility with the cement particles can be improved.

The reactive surfactant may be included in an amount of 0.05% by weight to 1.0% by weight based on the total weight of the cement admixture composition. When the above-mentioned range is satisfied, an effect of improving the bonding force and the fracture property with the cement particles is exhibited.

The weight average molecular weight of the carboxylic acid-based copolymer according to the present invention is preferably 10,000 to 100,000. When the weight-average molecular weight is 10,000 to 100,000, the flowability is excellent, the slump retention of the composition is maintained, and the fluidity is prevented from lowering, and a concrete composition having high strength can be formed early.

The unsaturated polyalkylene glycol ether monomer represented by Formula 1 may be contained in an amount of 10% by weight to 50% by weight based on the total weight of the cement admixture composition. For example, in one embodiment, the monomer of Formula 1 may comprise from 10% to 45%, such as from 15% to 40% by weight, such as from 20% to 40% by weight, 25% by weight to 40% by weight.

The unsaturated carboxylic acid monomer represented by Formula 2 may be contained in an amount of 1 wt% to 10 wt% based on the total weight of the cement admixture composition. For example, in one embodiment, the monomer of Formula 2 may comprise from 1 wt% to 8 wt%, such as from 2 wt% to 5 wt%.

The acrylate monomer may be contained in an amount of 0.1% by weight to 5.0% by weight based on the total weight of the cement admixture composition. For example, in one embodiment, the acrylate-based monomer may be present in an amount ranging from 0.1 wt% to 4.0 wt%, such as from 0.1 wt% to 3.0 wt%, such as from 0.1 wt% to 2.0 wt% 0.1% by weight to 1.0% by weight.

 According to one embodiment of the present invention, there is provided an unsaturated polyalkylene glycol ether-based monomer represented by the following formula (1) and an unsaturated carboxylic acid monomer represented by the following formula (2); And a carboxylic acid-based copolymer polymerized from an acrylate-based monomer,

The present invention also provides a method for preparing a cement admixture composition comprising a peroxide and a reducing agent as a catalyst and comprising a reactive surfactant.

[Chemical Formula 1]

C _m H _2m-1 O (C _n H _2n O) _k (R ¹ O) ₁ R ²

(2)

In formula (1), R ¹ O is one or more oxyalkylene groups having 2 to 10 carbon atoms, R ² is hydrogen or an alkyl group having 1 to 20 carbon atoms,

m is from 2 to 4, n is from 3 to 6, k is 0 or 1, 1 is an average addition molar number of oxyalkylene groups of 1 to 1,000,

In Formula (2), R ³ to R ⁵ are each independently hydrogen, an alkyl group having 1 to 10 carbon atoms, a sulfone group, a carboxyl group, or a combination thereof, M is hydrogen, a monovalent metal, a divalent metal, Or an organic amine group.

According to one embodiment, the peroxide is hydrogen peroxide, and the reducing agent may be L-ascorbic acid or erythorbic acid, but is not limited thereto.

The cement admixture according to the present invention has an excellent fluidity and slump retention ability as compared with the conventional cement admixture and can provide a sufficient cement admixture and can shorten the production time, thereby providing a cement admixture composition having improved productivity have.

The invention will be described in more detail in the following examples. However, the following examples are illustrative of the present invention, and the present invention is not limited by the following examples.

Production Example 1: Preparation of cement admixture composition

Example 1

94 g of water, 94 g of 1,4-butanediol vinyl ether (average molar number of moles of ethylene oxide: 50 moles), and 30 g of water were added to a 2 L four-neck flask glass reactor equipped with a stirrer, a thermometer and a condenser. % Hydrogen peroxide, and after the temperature stabilized at 40 ° C., 14 g of acrylic acid, 1.4 g of 2-hydroxyethyl methacrylate, 63 g of water and 3-mercaptopropionic acid ) And 0.8 g of L-ascorbic acid dissolved therein was added over 3 hours. After maintaining the reaction temperature at 40 캜 for 3 hours, the polymerization reaction was completed, and 0.3 g of the reactive surfactant was added thereto to prepare an admixture composition.

Example  2 to 6 and Comparative Example  1 to 3

The cement admixture compositions of Examples 2 to 6 and Comparative Examples 1 to 3 were prepared by mixing according to the compositions and contents shown in Table 1 below.

division Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Comparative Example 1 Comparative Example 2 Comparative Example 3 Unsaturated alcohol 1,4-butanediol vinyl ether 35 35 35 35 35 35 35 - - 2-methylprop-2-en-1-ol - - - - - - - 35 3-methyl-3-
buten-1-ol - - - - - - - - 35 Acrylic acid 5 5 5 5 5 5 5 5 5 acryl
Rate 2-Hydroxyethyl methacrylate 0.5 - - 0.5 - - - - - 2-hydroxypropyl methacrylate - 0.5 - - 0.5 - - - - Pentaerythritol triacrylate - - 0.5 - - 0.5 - - - Chain Transfer Agent 3-Mercapto
propionic acid (3-MPA) 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 peroxide Hydrogen peroxide water 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 reducing agent L-ascorbic acid 0.3 0.3 0.3 - - - - - - Erythorbic acid - - - 0.3 0.3 0.3 0.3 0.3 0.3 Reactivity
Emulsifier Actylene glycol 0.1 0.1 0.1 0.1 0.1 0.5 - - - Water 58.1 58.1 58.1 58.1 58.1 57.7 58.7 58.7 58.7

(Unit: wt%)

Production Example 2: Production of Cement

The cement admixture composition according to any one of Examples 1 to 6 and Comparative Examples 1 to 3 was used in an amount of 0.1 wt% to 1 wt% relative to cement while maintaining the mixing ratio (W / C) of cement and water at 30% to 40% After mixing for 1 minute with a mixer, the mixture was allowed to stand under constant temperature and humidity conditions for 2 minutes, and cement was prepared.

Rating 1

The cement paste containing the cement admixture compositions of Examples 1 to 6 and Comparative Examples 1 to 3 was placed in a concrete slump to measure the flow (in mm) of the cement paste flowing during the slump removal. The concrete slump flow after 1 hour was measured by using the prepared cement for 1 hour.

The slump flow results measured as described above are shown in Table 2 below.

pH Viscosity Slump flow (mm) Early After 1 hour Example 1 3.22 40.4 225 230 Example 2 3.01 40.8 235 240 Example 3 2.98 42.1 230 240 Example 4 3.11 40.1 230 230 Example 5 3.01 40.9 225 230 Example 6 3.12 41.3 235 230 Comparative Example 1 3.14 40.9 190 200 Comparative Example 2 3.01 40.6 190 195 Comparative Example 3 2.99 39.3 185 180

The results of Table 2 show that the cement to which the cement admixture composition according to the embodiment of the present invention is applied exhibits a relatively high initial fluidity as compared with the cements of Comparative Examples 1 to 3 which do not contain a reactive surfactant , And the slump retention was relatively high.

This shows that the cement admixture of the present invention improves the dispersibility of the cement particles, thereby increasing the fluidity of the cement composition even at a small addition amount, and imparting good workability to the cement composition to form cement having high strength .

Claims (9)

10% by weight to 50% by weight of an unsaturated polyalkylene glycol ether monomer represented by the following formula (1); 1 to 10% by weight of an unsaturated carboxylic acid monomer represented by the following formula (2); And 0.1 to 5.0% by weight of an acrylate monomer, and an acetylenic reactive surfactant having a terminal hydrophilic group,
The unsaturated polyalkylene glycol ether monomer represented by the following formula (1) is at least one selected from the group consisting of polyethylene glycol vinyl ether, polypropylene glycol vinyl ether, and polybutylene glycol vinyl ether.
Cement admixture composition:
[Chemical Formula 1]
C _m H _2m-1 O (C _n H _2n O) _k (R ¹ O) ₁ R ²
(2)

In formula (1), R ¹ O is one or more oxyalkylene groups having 2 to 10 carbon atoms, R ² is hydrogen or an alkyl group having 1 to 20 carbon atoms,
m is from 2 to 4, n is from 3 to 6, k is 0 or 1, 1 is an average addition molar number of oxyalkylene groups of 1 to 1,000,
In Formula (2), R ³ to R ⁵ are each independently hydrogen, an alkyl group having 1 to 10 carbon atoms, a sulfone group, a carboxyl group, or a combination thereof, M is hydrogen, a monovalent metal, a divalent metal, Or an organic amine group.
delete delete The method according to claim 1,
The unsaturated carboxylic acid monomer represented by Formula 2 may be at least one selected from the group consisting of cement containing at least one of acrylic acid, methacrylic acid, maleic acid, maleic anhydride, crotonic acid, citraconic acid, citraconic anhydride, itaconic anhydride, ≪ / RTI > The method according to claim 1,
Wherein the acrylate-based monomer comprises a hydroxyl group, a carboxyl group or a salt thereof. The method according to claim 1,
Wherein the polymerized carboxylic acid-based copolymer has a weight average molecular weight of 10,000 to 100,000. The method according to claim 1,
Wherein the reactive surfactant comprises 0.05% by weight to 1.0% by weight based on the total weight of the cement admixture composition. delete 10% by weight to 50% by weight of an unsaturated polyalkylene glycol ether monomer represented by the following formula (1); 1 to 10% by weight of an unsaturated carboxylic acid monomer represented by the following formula (2); And 0.1 to 5.0% by weight of an acrylate monomer, the method comprising the steps of: preparing a cement admixture composition,
An acetylenic reactive surfactant containing a peroxide and a reducing agent as a catalyst and containing a hydrophilic group at the terminal thereof,
The unsaturated polyalkylene glycol ether monomer represented by the following formula (1) is at least one selected from the group consisting of polyethylene glycol vinyl ether, polypropylene glycol vinyl ether, and polybutylene glycol vinyl ether.
Preparation method of cement admixture composition:
[Chemical Formula 1]
C _m H _2m-1 O (C _n H _2n O) _k (R ¹ O) ₁ R ²
(2)

In formula (1), R ¹ O is one or more oxyalkylene groups having 2 to 10 carbon atoms, R ² is hydrogen or an alkyl group having 1 to 20 carbon atoms,
m is from 2 to 4, n is from 3 to 6, k is 0 or 1, 1 is an average addition molar number of oxyalkylene groups of 1 to 1,000,
In Formula (2), R ³ to R ⁵ are each independently hydrogen, an alkyl group having 1 to 10 carbon atoms, a sulfone group, a carboxyl group, or a combination thereof, M is hydrogen, a monovalent metal, a divalent metal, Or an organic amine group.