KR20120035563A - Polymer for early strength concrete admixture and method for preparing the same - Google Patents

Abstract

PURPOSE: A copolymer for early-strength concrete admixture is provided to obtain early-strength because of the reduction of unit number according to high strength and high durability, thereby reducing construction period. CONSTITUTION: A copolymer comprises 10-60 parts by weight of one or more kinds of unsaturated (meth)polyoxyalkylene urethane compounds in chemical formula 1, 5-30 parts by weight of one or more kinds of amine compounds in chemical formula 2, and 10-40 parts by weight of one or more kinds of unsaturated anionic organic compounds in chemical formula 3. The weight average molecular weight(Mw) of the copolymer is 5,000-150,000. The (meth)polyoxyalkylene urethane compound in chemical formula 1 is manufactured by adding urethane derivative-polyoxyalkylene. A concrete admixture comprises the copolymer.

Description

POLYMER FOR EARLY STRENGTH CONCRETE ADMIXTURE AND METHOD FOR PREPARING THE SAME}

The present invention relates to a copolymer for concrete admixtures having a new chemical structure and to concrete admixtures including the same, and more particularly to (meth) polyoxyalkylene urethane compounds (a), unsaturated amine compounds (b) and unsaturated anions The present invention relates to a copolymer for concrete admixtures comprising a urethane group and an amine group containing an active compound (c), and a concrete admixture for early strength development comprising the copolymer.

Concrete admixtures are additives for improving performance in concrete compositions such as cement paste, mortar, concrete, and the like, and are widely used as water reducing agents and fluidizing agents, and are mainly used for construction of structures in the field of civil construction. The concrete admixture has a property of having a large surface tension, and therefore, does not adversely affect the physical properties of the concrete body even when added as an additive, and thus increases strength. Therefore, concrete admixtures are currently recognized in the field of structural construction as an essential component to be added to concrete compositions.

Types of concrete admixtures currently in use include polycarboxylic acids or sulfates of naphthalene, melamine or lignin. Among the existing concrete admixtures, naphthalene-based, melamine-based, and lignin-based concrete admixtures are used in the form of sulphate. When the sulphate-type admixture is used in marine concrete, the deterioration of the structure is caused by the sulphate cracking. There is a problem that promotes. On the other hand, polycarboxylic acid-based polymer concrete admixtures have higher sensitivity and fluidity than conventional lignin-based admixtures or polynaphthalene sulfonic acid-based concrete admixtures, but they have a small blocking effect on the penetration of chloride, but are difficult to completely block. .

On the other hand, in the field of civil construction, the necessity of high-rise buildings is emerging to solve population growth and limited topographical constraints, and focuses on reducing construction costs due to the shortening of construction period by the builders. Therefore, it is important to have early strength development characteristics when constructing a concrete composition. Conventional polycarboxylic acid-based concrete admixtures, although excellent in water-resistance and fluidity compared to the sulphate-type admixtures, it is still insufficient in the early strength of the concrete structure after construction.

Therefore, as a solution to this, what is currently used to promote early strength development of concrete structures are inorganic metal chloride additives such as calcium chloride or amine organic additives. Inorganic metal chloride additives promote early strength development of concrete structures, but the chloride content of concrete components increases the durability of concrete structures, and amine-based organic additives have insufficient early strength development and excessive usage. This adversely affects the physical properties of the concrete composition. Therefore, the necessity of a new kind of concrete admixture for early strength development is emerging.

Meanwhile, as an example of a conventional polycarboxylic acid concrete admixture, Japanese Patent Application Laid-Open No. 10-0003085 includes 20 mol% to 60 mol% of an alkyl (meth) acrylate compound and 15 mol% to 40 mol% of a polyalkylene glycol unsaturated compound. Polycarboxylic acid concrete admixtures having a weight average molecular weight of 20,000 or less have been disclosed.

JP-A-59-18338 discloses a cement dispersant prepared by copolymerization of a polyalkylene glycol mono (meth) acrylate ester compound and a (meth) acrylic acid compound. The cement dispersant disclosed in the specification of the patent document has a polyalkylene glycol chain and lowers the cohesive adsorption force of the cement particles, so that the dispersibility is good, while the cement coagulation delay effect is weak.

U.S. Patent No. 5,661,206 uses a copolymer of a polycarboxylic acid compound and a copolymer of an alkoxy polyalkylene glycol mono (meth) arylether compound and a polycarboxylic acid compound as a fluidizing agent to increase the fluidity of the cement slurry, It is disclosed that the slump reduction problem can be solved.

In addition, Japanese Laid-Open Patent Publication No. 2003-0065580 discloses the ability of a concrete composition to be used as an ultrahigh strength concrete admixture using an unsaturated polyethyleneimine EO adduct compound and an unsaturated organic acid compound in which an unsaturated bond is introduced as an unsaturated organic acid into the polyethyleneimine EO adduct. It also suggests that workability can be improved.

However, the concrete admixtures disclosed in the above patent documents exhibit relatively high sensitivity, while increasing the viscosity of the concrete composition, resulting in poor workability, and improving the long-term strength of the concrete composition, but insufficient early strength development. .

Therefore, the problem to be solved by the present invention is a polycarboxylic acid-based copolymer that can be applied as a concrete admixture that not only has a high sensitivity but also improves workability and promotes hydration reaction of the concrete composition to promote early strength. And to provide a concrete admixture comprising the same.

One embodiment of the present invention is at least one unsaturated (meth) polyoxyalkylene urethane compound of formula (a), at least one unsaturated amine compound (b) of formula (2), and at least one formula (3) A copolymer of unsaturated anionic organic compound (c) is provided.

Formula 1

In Chemical Formula 1, X ₁ , Y ₁ and Z ₁ are the same as or different from each other independently, and each is hydrogen (-H), methyl group (-CH ₃ ) or carboxylic acid group (-COOH), and R ₁ is carbon number 1 Is a hydrocarbon group or ketone group of 6 to 6, R ₂ is an aromatic group having 6 carbon atoms, a cyclic hydrocarbon group having 3 to 12 carbon atoms or a hydrocarbon group having 1 to 6 carbon atoms, R ₃ is hydrogen (-H), or 1 to and 6 a hydrocarbon group, P _l O is an alkyl of 1 2 to 20 carbon atoms or more species oxy group, m is from 2 to 100 constant as the mean molecular number of added oxyalkylene group, n is an average addition mole number of the repeating units 1 Is an integer from 50 to 50, and the average number of moles (m * n + m) of the total oxyalkylene groups is an integer from 50 to 100.

Formula 2

In Formula 2, X ₂ , Y ₂ and Z ₂ are the same as or different from each other independently, and are each selected from the group consisting of hydrogen (—H), methyl group (—CH ₃ ), provided that X ₂ , Y ₂ and Z Any one of ₂ is hydrogen, R ₄ is a hydrocarbon group or ketone group having 1 to 6 carbon atoms, R ₅ is a hydrocarbon group having 1 to 6 carbon atoms, and R ₆ , R ₇ are the same as or different from each other independently, Each selected from the group consisting of hydrogen (-H), hydroxyl (-OH), or an alkyl alcohol group having 1 to 6 carbon atoms.

Formula 3

In Formula 3, X ₃ , Y ₃ and Z ₃ are the same as or different from each other independently, and are each selected from the group consisting of hydrogen (-H), methyl group (-CH ₃ ) and carboxylic acid group (-COOH), Provided that any one of X ₃ , Y ₃ and Z ₃ is hydrogen; And R ₈ represents a carboxylic acid group (-COOH) or a nitrile group (-CN).

Copolymer according to an embodiment of the present invention is also 10 parts by weight to 60 parts by weight of the unsaturated (meth) polyoxyalkylene urethane compound (a) of Formula 1, 5 parts by weight of the unsaturated amine compound (b) of Formula 2 Part to 30 parts by weight and 10 to 40 parts by weight of the unsaturated anionic organic compound (c) of the formula (3).

The copolymer according to the embodiment of the present invention has a weight average molecular weight (Mw) of 5,000 to 150,000.

In addition, in Chemical Formula 1, m may be 6 to 50.

The unsaturated (meth) polyoxyalkylene urethane compound of Formula 1 may be prepared by adding an unsaturated organic acid and a urethane derivative-polyoxyalkylene.

The unsaturated amine compound of Formula 2 may be prepared by adding an unsaturated organic acid and an amine derivative.

The unsaturated anionic organic compound of Formula 3 may be acrylic acid, methacrylic acid, maleic acid, itaconic acid, citraconic acid, fumaric acid; It may be selected from the group consisting of monovalent metal salts thereof, divalent metal salts, ammonium groups, organic amine groups and anhydrides thereof.

According to one embodiment of the present invention, at least one unsaturated (meth) polyoxyalkylene urethane compound (a) of Formula 1, at least one unsaturated amine compound (b) of Formula 2, and at least one It provides a concrete admixture comprising a copolymer of unsaturated anionic organic compound of formula (c).

Formula 1

In Chemical Formula 1, X ₁ , Y ₁ and Z ₁ are the same as or different from each other independently, and each is hydrogen (-H), methyl group (-CH ₃ ) or carboxylic acid group (-COOH), and R ₁ is carbon number 1 Is a hydrocarbon group or ketone group of 6 to 6, R ₂ is an aromatic group having 6 carbon atoms, a cyclic hydrocarbon group having 3 to 12 carbon atoms or a hydrocarbon group having 1 to 6 carbon atoms, R ₃ is hydrogen (-H), or 1 to and 6 hydrocarbon group, P _l O is an alkyl of 1 2 to 20 carbon atoms or more species oxy group, m is from 2 to 100 constant as the mean molecular number of added oxyalkylene group, n is an average addition mole number of the repeating units 1 Is an integer from 50 to 50, and the average number of moles (m * n + m) of the total oxyalkylene groups is an integer from 50 to 100.

Formula 2

In Chemical Formula 2, X ₂ , Y ₂ and Z ₂ are the same as or different from each other independently, and are each selected from the group consisting of hydrogen (—H) and methyl group (—CH ₃ ), provided that X ₂ , Y ₂ and Z Any one of ₂ is hydrogen, R ₄ is a hydrocarbon group or ketone group having 1 to 6 carbon atoms, and R ₅ is a hydrocarbon group having 1 to 6 carbon atoms; And R ₆ , R ₇ are the same or different independently from each other, and are each selected from the group consisting of hydrogen (-H), hydroxyl (-OH), or an alkyl alcohol group having 1 to 6 carbon atoms.

Formula 3

In Formula 3, X ₃ , Y ₃ and Z ₃ are the same as or different from each other independently, and are each selected from the group consisting of hydrogen (-H), methyl group (-CH ₃ ) and carboxylic acid group (-COOH), Provided that any one of X ₃ , Y ₃ and Z ₃ is hydrogen; And R ₈ represents a carboxylic acid group (-COOH) or a nitrile group (-CN).

Concrete admixture according to an embodiment of the present invention is 10 to 60 parts by weight of the unsaturated (meth) polyoxyalkylene urethane compound (a) of Formula 1, 5 parts by weight of unsaturated amine compound (b) of Formula 2 To 30 parts by weight and 10 to 40 parts by weight of the unsaturated anionic organic compound (c) of the formula (3).

The weight average molecular weight (Mw) of the copolymer included in the concrete admixture is 5,000 to 150,000. In addition, m in Formula 1 may be 6 to 50.

The unsaturated (meth) polyoxyalkylene urethane compound of Formula 1 may be prepared by adding an unsaturated organic acid and a urethane derivative-polyoxyalkylene.

The unsaturated amine compound of Formula 2 may be prepared by adding an unsaturated organic acid and an amine derivative.

The unsaturated anionic organic compound of Formula 3 may be acrylic acid, methacrylic acid, maleic acid, itaconic acid, citraconic acid, fumaric acid; It may be selected from the group consisting of monovalent metal salts thereof, divalent metal salts, ammonium groups, organic amine groups and anhydrides thereof.

Concrete admixture according to the present invention can reduce the construction period and early strength of the concrete structure through the reduction of unit quantity and early strength according to the high strength, high durability of the concrete.

1 is a graph of the total organic carbon analysis of the copolymers prepared in Example 1 and Comparative Example 1, (a) the total organic carbon analysis of the copolymer prepared in Example 1, (b) prepared in Comparative Example 2 Total organic carbon analysis of one copolymer.

As used herein, the term 'concrete composition' refers to a mixture of various components including cement, water, etc. for producing a concrete construction body, and is used herein interchangeably with 'cement composition'.

The present invention provides a polymerization initiator (d) for a compound containing at least one unsaturated (meth) polyoxyalkylene urethane compound (a), at least one unsaturated amine compound (b) and at least one unsaturated anionic compound (c). ), And copolymers obtained by polymerizing together with early strength developing concrete admixtures comprising the same.

The copolymer according to the present invention can be basically referred to as a ternary copolymer, and other compounds can be copolymerized together as long as the above-mentioned three compounds are copolymerized. That is, the copolymer according to the present invention is not limited to the above-mentioned tertiary copolymer, and other compounds which may be copolymerized with these compounds in addition to the above-mentioned three compounds may be added together and copolymerized. When compounds other than the above-mentioned three compounds are copolymerized together, it is preferable that the above-mentioned three compounds are the main components in the constituents of the compound to be copolymerized.

Each of the three compounds mentioned above may be used alone or in combination of two or more thereof. The copolymer for the early strength-expressing concrete admixture containing the compound is a copolymer having a structure in which (meth) polyoxyalkylene urethane is bonded to the main chain as a side chain and an amine compound is bonded to the main chain, It is a copolymer containing (meth) polyoxyalkylene urethane and in which an amine compound exists in a principal chain.

The copolymer according to the present invention is a (meth) polyoxyalkyl which is a nonionic hydrophilic group having steric hindrance contained in a repeating unit derived from the unsaturated (meth) polyoxyalkylene urethane compound (a) of the formula (1). The len group gives the hydrophilicity and the dispersibility of the concrete composition. In addition, the copolymer according to the present invention is due to the amine group contained in the repeating unit derived from the unsaturated amine compound (b) of formula (2) so that the copolymer can have the property of promoting the hydration reaction of the cement in the concrete composition In addition, the anionic group contained in the repeating unit derived from the unsaturated anionic compound (c) of Formula 3 allows the copolymer to have a better adsorption property on the surface of the cement particles in the concrete composition. In addition, the effect of the present invention can be exhibited by limiting the polymerization composition ratio of the compound as described above.

Specifically, the copolymer for early strength-expressing concrete admixtures according to the present invention is 10 parts by weight to 60 parts by weight of at least one unsaturated (meth) polyoxyalkylene urethane compound (a) in a compound having an anionic group as a unit compound, unsaturated 5 to 30 parts by weight of the amine compound (b) and 10 to 40 parts by weight of the unsaturated anionic compound (c).

The weight average molecular weight (Mw) of the copolymer for early strength-expressing concrete admixtures is preferably 5,000 to 150,000. When the weight average molecular weight is less than 5,000, the initial dispersibility of the cement and concrete composition is remarkably poor, and workability is not improved. When the weight average molecular weight is more than 150,000, the dispersion retention over time of the cement and concrete composition is sufficient. It may not be improved and may not provide sufficient workability.

The weight average molecular weight of the copolymer for early strength-expressing concrete admixtures is a weight average molecular weight measured by Gel Permeation Chromatography (hereinafter referred to as "GPC"), and is expressed in polyethylene glycol equivalents. It is preferable to measure by the following GPC measurement conditions.

GPC  Molecular Weight Measurement Condition

Use column: Ultrahydrogel Linear + Ultrahydrogel 120PKGD Waters

Eluent: a solution of 5 g of sodium nitrate dissolved in 1,000 g of water

Flow rate of eluent: 0.8 ml / min

Column temperature: 40 ℃

Standard samples: Poly Ethylene Glycol, peak-top molecular weight (Mp) 272500, 219300, 85000, 46000, 24000, 12600, 7100, 4250 and 1470

Detector: Waters differential refractive index detector

Hereinafter, the compounds constituting the compound component of the copolymer according to the present invention will be described in detail.

(1) unsaturated ( MET ) Polyoxyalkylene  Urethane Compound (a)

Unsaturated (meth) polyoxyalkylene urethane compound (a), which is one of the components constituting the copolymer for the early strength-expressing concrete admixture according to the present invention, contains a polymerizable unsaturated functional group, a urethane derivative and an oxyalkylene chain, and It is a structure connected by a bond, it can be represented by the following formula (1).

Formula 1

In Chemical Formula 1, X ₁ , Y ₁ and Z ₁ are the same as or different from each other independently, and each is hydrogen (-H), methyl group (-CH ₃ ) or carboxylic acid group (-COOH), and R ₁ is carbon number 1 Is a hydrocarbon group or ketone group of 6 to 6, R ₂ is an aromatic group having 6 carbon atoms, a cyclic hydrocarbon group having 3 to 12 carbon atoms or a hydrocarbon group having 1 to 6 carbon atoms, R ₃ is hydrogen (-H), or 1 to and 6 hydrocarbon group, and P _l O is one kind or two kinds of a carbon number of 2 to 20 or more oxyalkylene group, m is an integer from 2 to 100 as a mean molecular number of added oxyalkylene group, n is the average addition the repeating unit It is an integer of 1-50 as molar number, and the average added mole number (m * n + m) of the total oxyalkylene group in an unsaturated (meth) polyoxyalkylene urethane compound is an integer of 50-100.

The unsaturated (meth) polyoxyalkylene urethane compound (a) has a polyoxyalkylene-urethane derivative chain having an average added mole number n of 1 to 50 moles. When the average added mole number is within the above range, the unsaturated (meth) polyoxyalkylene urethane compound (a) can sufficiently provide the steric hindrance effect function in the cement composition. More preferably, the average added mole number of the said repeating unit is 3 mol-30 mol.

In Formula 1 is an oxyalkylene group of the alkylene oxide addition product alone or in combination of two or more of 2 to 20 carbon atoms represented by P _l O. Such alkylene oxide adducts have a structure derived from one or two or more alkylene oxides such as ethylene oxide, propylene oxide, butylene oxide and isobutylene oxide.

The P _l O by one or more, alone or in combination of two or represent oxyalkylene groups any added in the same unsaturated (meth) polyoxyalkylene urethane compound (a) method, i.e., random addition, block addition, the addition by alternately adding Can be. If the P _l O is made up of two or more oxyalkylene groups, these may be added to add or irregular, into blocks.

Average addition mol number (m) of the oxyalkylene group represented by the above-mentioned _l P O is preferably an integer of 2 to 100. When m is less than 2, the flexibility of the chain is poor, and a steric hindrance sufficient to disperse the cement particles and the like cannot be obtained, and the hydrophilicity of the oxyalkylene group may be insufficient to show the dispersing force. If m is greater than 100, the dispersion retention performance of the cement and concrete composition is poor over time, and workability cannot be sufficiently improved. More preferably, the average added mole number (m) of the said oxyalkylene group is 6-50. When the average added mole number (m) of the oxyalkylene group is in the above range, the flexibility and hydrophilicity of the chain may be improved to sufficiently improve the initial dispersion of the cement and concrete compositions and the retention of dispersion over time, thereby improving workability. .

Examples of the compound of Formula 1 include unsaturated organic acid-polyoxyalkylene urethane adducts. The unsaturated organic acid-polyoxyalkylene urethane adduct may be any compound having a structure in which a polyoxyalkylene urethane chain is added to an organic acid containing an unsaturated group.

An unsaturated organic acid-polyoxyalkylene urethane addition reaction, which is one example of a method of preparing the compound of Formula 1, may be briefly described with reference to Scheme 1 below.

Scheme 1

In Scheme 1, R 'is a hydrogen group or a methyl group, R "is a hydroxyl group (-OH), or an oxyhydrocarbon group having 1 to 6 carbon atoms, m is an integer of 2 to 100, n is an integer of 1 to 50 to be.

Referring to Scheme 1, the urethane derivative and the diol are added to produce a urethane compound, and then the resulting urethane compound is reacted with an unsaturated organic acid or unsaturated alcohol. Examples of the urethane derivatives include diisocyanate derivatives having aromatic hydrocarbon groups, cyclic hydrocarbon groups or linear hydrocarbon groups. Diisocyanate derivatives having aromatic, cyclic or linear hydrocarbon groups are more specifically, for example, 2,4-toluene diisocyanate, methylenediphenyl-4,4'-diisocyanate, tetramethyl-1,3-xylene di Isocyanate, para-phenylene diisocyanate, 1,6-hexamethylene diisocyanate, 1,5-naphthalene diisocyanate, isopron diisocyanate or cyclohexylmethane diisocyanate.

In addition, examples of the diol include polyethylene glycol, propylene glycol, or butylene glycol isobutylene glycol.

Examples of unsaturated organic acids that can be used in the reaction include, for example, monocarboxylic acids such as acrylic acid, methacrylic acid; And dicarboxylic acids such as maleic acid, itaconic acid, citraconic acid, fumaric acid, and the like, and monovalent metal salts, divalent metal salts, ammonium salts or organic amine salts thereof, or anhydrides thereof. As an unsaturated alcohol, it is vinyl alcohol, (meth) allyl alcohol, 3-butene-1-ol, isoprene alcohol, 3-methyl-2- buten-1-ol, 2-methyl-3- butene-1-, for example. Ol, 2-methyl-3-buten-2-ol, 2-methyl-2-buten-1-ol and the like.

The unsaturated (meth) polyoxyalkylene urethane compound (a) is included in an amount of 10 parts by weight to 60 parts by weight when preparing a copolymer for early strength-expressing concrete admixture of the present invention. When the content of the unsaturated (meth) polyoxyalkylene urethane compound (a) is less than 10 parts by weight, the susceptibility and workability of the concrete composition cannot be sufficiently improved, and the unsaturated (meth) polyoxyalkylene urethane compound When the proportion of the structural unit derived from (a) is more than 60 parts by weight, there is not enough adsorber capable of adsorbing to the surface of the cement particles, resulting in poor initial dispersion performance of the cement and concrete composition. More preferably, the ratio is 30 parts by weight to 60 parts by weight.

The unsaturated organic acid-polyoxyalkylene urethane compound is a nonionic hydrophilic compound having both a hard portion such as a urethane derivative group and a soft portion such as polyethylene glycol, and is a side chain in the copolymer for concrete admixture according to the present invention. Exists as.

(2) unsaturated Amine  Compound (b)

Unsaturated amine compound (b), which is one of the components constituting the copolymer for early strength-expressing concrete admixtures according to the present invention, contains a polymerizable unsaturated group and an amine functional group and is connected by an ester bond. Indicates.

Formula 2

In Chemical Formula 2, X ₂ , Y _2, and Z ₂ are the same as or different from each other independently, and are each hydrogen (—H) or a methyl group (—CH ₃ ), provided that any one of X ₂ , Y _2, and Z ₂ is Hydrogen, R ₄ is a hydrocarbon group or ketone group having 1 to 6 carbon atoms, R ₅ is a hydrocarbon group having 1 to 6 carbon atoms, and R ₆ and R ₇ are the same as or different from each other independently, and each hydrogen (-H ), A hydroxyl group (-OH), and an alkyl alcohol group having 1 to 6 carbon atoms.

The unsaturated amine compound (b) represented by the formula (2) is, for example, an unsaturated organic acid-amine compound. The unsaturated organic acid-amine compound may be any compound having a structure in which the organic amine compound is added to an organic acid containing an unsaturated group.

The compound of Formula 2 may be prepared according to the method illustrated in Scheme 2 below, for example, by an unsaturated organic acid-amine compound addition reaction.

In Scheme 2, R ¹⁰⁰ is a hydrogen group (-H) or a methyl group (-CH ₃ ), and R ¹⁰¹ is a hydrogen group (-H) or an oxyalkylene group.

Referring to Scheme 2, an unsaturated organic acid-organic amine adduct is obtained by esterifying an unsaturated organic acid or unsaturated alcohol with an organic amine.

Examples of the organic amine used to prepare the unsaturated organic acid-organic amine adduct include an organic amine derivative in which a hydroxyl group or a linear alkyl alcohol is added to the amine. More specifically, examples of the organic amine derivative having a hydroxyl group or a linear alkyl alcohol include, for example, diethanolamine, triethanolamine, diethanol isopropanol amine, ethanol isopropanol amine, diisopropanol ethanol amine, triisopropanol amine, and the like. It is not limited to this.

In addition, examples of the unsaturated organic acid that can be used in the reaction include, for example, monocarboxylic acids such as acrylic acid and methacrylic acid; And dicarboxylic acids such as maleic acid, itaconic acid, citraconic acid, fumaric acid and the like, and monovalent metal salts, divalent metal salts, ammonium salts or organic amine salts thereof, or anhydrides thereof, and as the unsaturated alcohol, For example, vinyl alcohol, (meth) allyl alcohol, 3-butene-1-ol, isoprene alcohol, 3-methyl-2-buten-1-ol, 2-methyl-3-buten-1-ol, 2- Methyl-3-buten-2-ol and 2-methyl-2-buten-1-ol and the like are suitable.

The unsaturated amine compound (b) is included in an amount of 5 parts by weight to 30 parts by weight when preparing a copolymer for early strength-expressing concrete admixture of the present invention. When the content of the unsaturated amine compound (b) is less than 5 parts by weight, the early strength of the concrete composition may not be sufficiently improved, and when more than 30 parts by weight, the susceptibility and workability of the concrete composition may be sufficiently improved. none. More preferably, the content of the unsaturated amine compound (b) is 15 parts by weight to 25 parts by weight.

An unsaturated amine compound (b), such as the unsaturated organic acid-organic amine adduct, is a compound in which a polymerizable unsaturated group and a side chain-containing organic amine are present at the same time, and a portion derived from the unsaturated amine compound (b). Contributes to the early strength development of the concrete composition in the copolymer for concrete admixtures according to the invention.

(3) unsaturated Anionic  Organic compound (c)

The unsaturated anionic organic compound (c) of the present invention may be any of compounds having a polymerizable unsaturated group and a group capable of forming an anion. Preferred are unsaturated carboxylic acid compounds or unsaturated nitrile compounds. This is represented by the following formula (3).

Formula 3

In Formula 3, X ₃ , Y ₃ and Z ₃ are the same as or different from each other independently, and are each selected from the group consisting of hydrogen (-H), methyl group (-CH ₃ ) and carboxylic acid group (-COOH), Provided that any one of X ₃ , Y ₃ and Z ₃ is hydrogen; And R ₈ represents a carboxylic acid group (-COOH) or a nitrile group (-CN).

The unsaturated anionic organic compound can be selected from the group consisting of, for example, unsaturated monocarboxylic acid compounds, unsaturated dicarboxylic acid compounds and unsaturated nitrile compounds.

The unsaturated monocarboxylic acid compound may be any of compounds having one unsaturated group and a functional group capable of forming a carboxylic acid anion in the molecule. Examples of the unsaturated monocarboxylic acid compound may be selected from acrylic acid and methacrylic acid, but are not limited thereto.

The unsaturated dicarboxylic acid compound may be any of compounds having one unsaturated group and two functional groups capable of forming carboxyl anions in the molecule. Examples of the unsaturated dicarboxylic acid compound may be selected from maleic acid, itaconic acid, citraconic acid, fumaric acid, and the like, and monovalent metal salts, divalent metal salts, ammonium salts or organic amine salts thereof, or anhydrides thereof. It is not limited thereto.

The unsaturated nitrile compound may be any of compounds having one unsaturated group and a nitrile group. As an example of the unsaturated nitrile compound, acrylonitrile may be selected, but is not limited thereto.

The unsaturated anionic organic compound (c) is 10 parts by weight to 40 parts by weight when preparing a copolymer for early strength-expressing concrete admixture of the present invention. If the unsaturated anionic organic compound (c) is less than 10 parts by weight, the polymer may not be sufficiently adsorbed to the cement particles, and if it exceeds 40 parts by weight, it may adversely affect the performance of maintaining the dispersion of concrete over time. More preferably, it is 15 weight part-30 weight part.

In addition, as the unit compound constituting the copolymer for the early strength-expressing concrete admixture according to the present invention, a fourth compound component other than the above three compounds or compounds (a, b and c) may be added. As such, when the fourth component is further included, the ratio is preferably 0 to 30 parts by weight. The case where a 4th component is not included is represented by 0 weight part.

(4) polymerization Initiator  (d)

The copolymer for early strength-expressing concrete admixtures is prepared by polymerizing the aforementioned two compounds (a, b and c) together with a polymerization initiator (d).

As the polymerization initiator, persulfate salt, hydrogen peroxide, benzoyl peroxide, azo compound, diacyl peroxide, alkyl hydroperoxide and the like are preferable. Such polymerization initiators may be used alone or in combination of two or more.

In preparing the copolymers according to the invention, the content of the polymerization initiator can be determined as known in the art .

(5) other components (e)

In addition, reducing agents may further be used as promoters. As the reducing agent, for example, sodium hydrogen sulfite, sodium sulfite, formaldehyde sodium sulfoxylate, potassium persulfate and ascorbic acid and the like and an amine compound such as ethylene diamine, sodium ethylene diamine tetra acetate and glycine Can be used. When the reducing agent is used, the amount thereof may be appropriately adjusted as known in the art.

Moreover, a chain transfer agent can be used as needed and can be used 1 type or in combination of 2 or more types. In the case of using the chain transfer agent, those skilled in the art can appropriately adjust the amount used according to the known contents in the art.

Hereinafter, a method for producing a copolymer for concrete admixtures according to the present invention by copolymerizing the three compounds or compounds (a, b and c) with the polymerization initiator (d) will be described.

Early strength development concrete of the present invention Admixture  Method of Preparation of Copolymer

The present invention also provides a method of copolymerizing the three compounds (a, b and c) together with the polymerization initiator (d) to produce a copolymer for early strength development concrete admixtures.

As a manufacturing method of the copolymer for the early strength expression concrete admixtures of this invention, the polymerization method like solution polymerization or bulk polymerization is mentioned.

The polymerization can be batch, continuous, or semi-continuous.

Non-limiting examples of solvents used when necessary for the polymerization step include water, alcohols, aromatic organic compounds, esters and ketones. Specific examples include methyl alcohol, ethyl alcohol, isopropyl alcohol, benzene, toluene, cyclohexane, xylene, n-heptane, ethyl acetate, acetone, methyl ethyl ketone and the like. These may be used alone, or two or more of them may be used in combination.

As a method of adding the compound component, a polymerization initiator, etc. to the reactor as an example of the above-mentioned polymerization method, a method of carrying out polymerization by charging all the compounds in the reactor and then dropping the polymerization initiator thereto; Charging some of the compound components into the reactor and then adding the polymerization initiator and the residual compound component thereto to effect polymerization; Or a method selected from a method in which a reactor is charged with a polymerization solvent, and then the total amount of the compound component and the polymerization initiator is added dropwise thereto.

The method includes a step of continuously adding and dropping a polymerization initiator and a compound component into a reactor to perform the polymerization, a method including performing a secondary polymerization in a batch manner after the continuous polymerization, or a batch type Preference is given to a process comprising performing secondary polymerization continuously after polymerization. This is because the molecular weight of the resulting copolymer can be made uniform, which can increase the water-resistance and fluidity in cement and concrete compositions comprising the copolymer as admixtures, thereby improving the retention of dispersion in the cement and concrete compositions. .

Copolymers for early strength development concrete admixtures, specifically, i) filling the reactor with a solvent; ii) at least one unsaturated (meth) polyoxyalkylene urethane compound of formula (a), at least one unsaturated amine compound (b) of formula (2), and at least one unsaturated of formula (3) Dropping the anionic organic compound (c) and the polymerization initiator (d); And iii) polymerizing the obtained reactant; Or i) at least one unsaturated (meth) polyoxyalkylene urethane compound of Formula 1 (a), at least one unsaturated amine compound of Formula 2 (b), at least one unsaturated of Formula 3 Charging at least one compound or compound component of the anionic organic compound (c) and a solvent; ii) dropping the remaining compound or compound component and the polymerization initiator (d); And iii) polymerizing the obtained reactant.

The method of preparing the copolymer for the early strength-expressing concrete admixture may further include neutralizing the copolymer obtained through the above step with an alkaline material. The alkaline material may be selected from among hydroxides, chlorides, ammonia and organic amines of monovalent and divalent metals, for example.

In the polymerization reaction, at least one accelerator (e) may be further used in addition to the polymerization initiator (d). As the accelerator (e), a reducing agent may be used. Description of the reducing agent is the same as described above, and overlapping content is omitted.

Moreover, a chain transfer agent can be used as needed and can be used 1 type or in combination of 2 or more types. As the chain transfer agent, a chain transfer agent known in the art may be easily selected and used.

In the polymerization method, the polymerization temperature and other polymerization conditions are preferably appropriately selected depending on the polymerization method, solvent, polymerization initiator and chain transfer agent used. Generally, the polymerization temperature is 40 ° C to 180 ° C. Specifically, it is 60 to 100 ° C. The polymerization reaction time also ranges from about 1 hour to about 24 hours. Specifically, it is 2 to 12 hours.

The copolymer for early strength-expressing concrete admixtures according to the present invention may be used by adding one or more kinds to the concrete composition. Preferably, the copolymer according to the invention can be added to the concrete composition as a concrete admixture, and can also be used with other concrete admixtures having a high sensitivity.

As an example of the concrete admixture having high water-resistance, a concrete admixture comprising essentially a copolymer for urethane derivative-polyethylene glycol chain admixture with an early strength-strengthening concrete admixture having a length of 3 mol or more is mentioned. The compound component for forming the copolymer for the early strength-expressing concrete admixture includes an anionic organic compound containing an unsaturated (methoxy) polyoxyalkylene urethane compound, an unsaturated amine compound and an unsaturated anionic group as essential components. The urethane derivative-polyethylene glycol chain length is preferably 3 mol or more, more preferably 6 to 150 mol, even more preferably 10 to 100 mol.

When the copolymer for concrete admixtures according to the present invention is used, the adsorption rate is high due to the large amount of anionic adsorber of the copolymer main chain portion on the surface of the cement particles even in the strong alkali state in the slurry of the concrete composition. Since the meth) polyoxyalkylene urethane derivative maintains steric reaction force, high sensitivity and workability can be ensured, and early strength can be expressed by promoting cement hydration reaction by an amine compound present in the main chain. Therefore, it is easy to control the flowability of the concrete exhibiting early strength according to the shortening direction of air, specifically, it has a high water-resistance and at the same time, the workability at the time of pouring even in a state where the water / cement ratio is lowered by the increase in water-resistance. It can increase, and also the early strength of the concrete structure can be expressed, thereby reducing the raw material cost in concrete construction. Therefore, it is possible to prevent the decrease of strength and material separation caused by increasing water / cement (W / C) ratio or adding excessive fluidizing agent, and to shorten the air by increasing the turnover rate during concrete pouring in winter. Raw material costs can be reduced. In addition, it is possible to improve the workability in the slurry state and to increase the long-term strength and durability of the concrete structure.

Although the present invention will be described in more detail with reference to the following examples, the above examples are for illustrative purposes, and the present invention is not limited to these examples.

Desaturation Poly  ( MET ) Oxyethylene  Urethane compound

120 g of 2,4-toluene diisocyanate, dibutyltin dilaurate 0.02 g polyethylene glycol (average added mole number: 45) in a 1 liter glass reactor equipped with thermometer, stirrer, dropping funnel, nitrogen suction tube and reflux condenser The reactor was purged with nitrogen under stirring and heated to 60 ° C. in a nitrogen atmosphere. After stirring for 3 hours, 18 g of methacrylic acid, a small amount of phenothiazine and 6 parts by weight of cyclohexane as a circulating solvent were added to a total weight part of the outer shell through a dropping funnel. Thereafter, the reaction is carried out at 100 ° C. for 12 hours. After completion of the reaction, the circulating solvent was removed by distillation under reduced pressure at 80 ° C., and then a poly (meth) oxyethylene urethane compound having an unsaturated group (molecular weight of urethane derivative-oxyethylene addition 45) was prepared.

Desaturation Amine  Compound manufacturing

Into a 1-liter glass reactor equipped with a thermometer, agitator, dropping funnel, nitrogen suction tube and reflux condenser, 102 g of ethanol diisopropanol amine, 170 g of methacrylic acid, a small amount of phenothiazine and cyclohexane, a circulating solvent, 6 parts by weight And stir. Thereafter, the reaction is carried out at 100 ° C. for 12 hours. After completion of the reaction to remove the circulating solvent through distillation under reduced pressure at 80 ℃, an amine compound having an unsaturated group was prepared.

Example  One

285 g of distilled water was charged to a glass 1 l reactor equipped with a thermometer, stirrer, dropping funnel, nitrogen suction line and reflux condenser. The inside of the reactor was purged with nitrogen under stirring and heated to 80 ° C. in a nitrogen atmosphere. Then, a mixture consisting of 170 g of unsaturated poly (meth) oxyethylene urethane compound (a, number of moles of urethane derivative-oxyethylene addition 45) prepared through the above reaction in the reactor, 75 g of unsaturated amine compound (b), 95 g of methacrylic acid, and 50 g of distilled water The solution was added dropwise over 5 hours. At the same time, an aqueous solution in which 0.85 g of ammonium persulfate was dissolved in 50 g of water was added dropwise thereto over 6 hours.

After completion of dropping, the reaction mixture was maintained at 80 ° C. for 1 hour. In addition, the copolymer for the early strength-expressing concrete admixture of the present invention having a weight average molecular weight of 41,000 when the pH of the reaction product was adjusted to 6 using sodium hydroxide and measured by gel permeation chromatography and expressed in terms of polyethylene glycol equivalent (S -1) was obtained.

Example  2 to Example  3

The copolymers (S-2) to (S-3) for early strength-expressing concrete admixtures were prepared in the same manner as in Example 1, except that the amount of the compound used was in the amount shown in Table 1 below.

Comparative example  One

285 g of distilled water was charged to a glass 1 L reactor equipped with thermometer, stirrer, dropping funnel, nitrogen suction tube and reflux condenser. The inside of the reactor was purged with nitrogen under stirring and heated to 80 ° C. in a nitrogen atmosphere. Then, a mixed solution consisting of 170 g of unsaturated polymethoxy polyethylene glycol monomethacrylate (mole number of oxyethylene addition 45), 75 g of unsaturated amine compound (b), 95 g of methacrylic acid, and 50 g of distilled water was added dropwise to the reactor over 5 hours. At the same time, an aqueous solution in which 0.85 g of ammonium persulfate was dissolved in 50 g of water was added dropwise thereto over 6 hours.

After completion of dropping, the reaction mixture was maintained at 80 ° C. for 1 hour. The comparative early strength-coating concrete admixture copolymer having a weight average molecular weight of 39,000 when measured by gel permeation chromatography and measured by gel permeation chromatography using sodium hydroxide (C- 1) was obtained.

Comparative example  2 to Comparative example  4

In the same manner as in Comparative Example 1, using the compound composition shown in Table 1 below, copolymers (C-2) to (C-4) for concrete admixtures for early strength expression were prepared.

Comparative example  5

A copolymer (C-5) for early strength-expressing concrete admixtures was prepared in the same manner as in Example 1 except that the type and content of the compound used were as described in Table 1 below.

Copolymer
No. Composition ratio of copolymer (parts by weight) Initiator menstruum Weight average molecular weight Example 1 S-1 POEU-45: ACM: MAA
= 50:22:28 APS water 41,000 Example 2 S-2 POEU-45: ACM: MAA
= 42:30:28 APS water 39,800 Example 3 S-3 POEU-45: ACM: MAA
= 60:10:30 APS water 41,000 Comparative Example 1 C-1 MPEG-45: ACM: MAA
= 50:22:28 APS water 39,000 Comparative Example 2 C-2 MPEG-45: ACM: MAA
= 42:30:28 APS water 41,000 Comparative Example 3 C-3 MPEG-45: ACM: MAA
= 60:10:30 APS water 38,000 Comparative Example 4 C-4 MPEG-45: MAA
= 70:30 APS water 35,700 Comparative Example 5 C-5 POEU-45: MAA
= 70:30 APS water 40,000

POEU-45: unsaturated (meth) polyoxyethylene urethane compound (a)

(Urethane derivative-oxyethylene average added mole number 45)

ACM: unsaturated amine compound (b)

MPEG-45: Unsaturated polymethoxypolyethylene glycol monomethacrylate (average added mole number 45 of ethylene oxide)

MAA: methacrylic acid (c)

APS: ammonium persulfate (polymerization initiator)

Test Example  1: Total Organic Carbon Analysis of Copolymers

In order to evaluate the strength of the adsorption force on the surface of the cement particles according to the aging change of the copolymers prepared in Examples 1 to 4 and Comparative Examples 1 to 4 using TOC (total organic carbon contents analyzer) Was performed.

Total organic carbon measurement analysis measured non-purgeable organic carbon (NPOC) using a Sievers InnovOx instrument (GE, USA). Cement paste experiments were performed under measurement conditions, and the test conditions were as follows.

Water / cement: 150%

Cement (Korea-Japan OPC): 700g

Admixture usage: 8.4g (1.2% of powder)

Agitation time: 120 seconds

Measuring interval: up to 120 minutes in 30 minute intervals

After obtaining the supernatant of the cement composition obtained through the above conditions through a centrifugal separator, the organic carbon measurement was performed after removing the foreign matter using a 0.45㎛ filter.

Through total organic carbon measurement, the results obtained are shown in FIG. 1. Referring to Figure 1, the measurement result of the copolymer for ultra-high strength concrete admixture prepared in Example 1 is a graph shown in (a), as can be seen from the graph, the initial adsorption rate is fast, the adsorption amount according to the change over time You will see a steady increase. On the contrary, the measurement result of the comparative ultra high strength concrete admixture prepared in Comparative Example 1 is a graph represented by (b), and as can be seen from the graph, the initial adsorption rate and It was confirmed that the adsorption amount was decreased due to changes over time. This phenomenon is because the electron attraction force of the carboxylic acid group present in the main chain is stronger than that of the copolymer prepared in the comparative example due to the electron donating phenomenon acting on the urethane derivative present in the unsaturated (meth) polyoxyethylene urethane compound (a). It seems to be.

Test Example  2: concrete test

The copolymers obtained in Examples 1 to 3 and Comparative Examples 1 to 5 were evaluated as concrete admixtures. The results are shown in Table 2. The results of the strength test of the concrete specimens by the above experiments are shown in Table 2. Concrete test conditions are as follows.

Concrete test conditions

Tap water: 130 kg / ㎥

Cement (Korea-Japan OPC): 448 kg / ㎥

Water / cement: 22%

Fine powder: fly ash 89 kg / m 3, silica fume 53 kg / m 3

Fine aggregates: 277 kg / m3 of silt, 508 kg / m3 of crushed sand

Assembly Aggregate: 25mm Gravel 974 kg / ㎥

Concrete admixture addition amount: 1.0% for Examples 1 to 3 and Comparative Example 5, 1.2% for Comparative Examples 1 to 4

(Comparative Examples 1 to 4 adjusts the usage amount to 1.2% in order to set the initial dispersing force to the same level as the Example)

The materials were mixed for 120 seconds with a forced pan mixer. Initial slump flow value was set to 50 ± 5 cm and measured immediately after mixing.

Copolymer
No. Resistant, Distributed Retention
Concrete condition (cm) Immediately 30 minutes 60 minutes 90 mins Example 1 S-1 57 54 52 50 Example 2 S-2 53 49 46 44 Example 3 S-3 58 55 48 42 Comparative Example 1 C-1 56 52 48 42 Comparative Example 2 C-2 48 42 36 - Comparative Example 3 C-3 53 52 44 39 Comparative Example 4 C-4 46 50 42 - Comparative Example 5 C-5 50 52 47 42

Referring to Table 2, the copolymer (S-1) to (S-3) prepared in Examples 1 to 3 (C-1) to (C-4) prepared in Comparative Examples 1 to 4 It can be seen that, despite the use of less than the amount of concrete admixtures, the same or more than the same water-resistance and dispersion retention. Therefore, when the copolymer according to the embodiment is used in the concrete composition as a concrete admixture, it can be confirmed that the concrete construct obtained has more excellent water-resistance and dispersion holding power than when the copolymer according to the comparative example is used.

From the above results, the urethane derivative-polyoxyalkylene chain which is present as a side chain in the copolymer prepared according to the example is steric in the concrete composition slurry state of the stronger alkali than the methoxy polyethylene glycol chain in the copolymer prepared according to the comparative example. It can be confirmed that the repulsive force is excellent to have a better dispersion holding power of the concrete composition. In addition, in Examples 1 to 3, the content of each of the compounds (a), (b) and (c) used as constituents was different, and it was confirmed that there was a difference in dispersion holding power during polymerization. That is, the more the content of the unsaturated (meth) polyoxyethylene urethane compound (a) component is included within the content range of the present invention, it can be seen that the sensitivity and dispersion retention improve.

Copolymer
No. Compressive strength (MPa)
(Concrete specimen curing temperature: 13 ℃) 18 hours 1 day 3 days 7 days 28 days Example 1 S-1 19.1 28.4 60.3 73.3 96.8 Example 2 S-2 20.1 29.1 61.2 74.2 97.5 Example 3 S-3 16.9 25.1 58.3 71.0 90.3 Comparative Example 1 C-1 15.4 21.2 54.2 68.1 87.2 Comparative Example 2 C-2 16.1 23.1 55.4 69.5 89.2 Comparative Example 3 C-3 10.1 19.7 49.2 65.2 83.2 Comparative Example 4 C-4 8.9 16.3 45.5 58.3 77.5 Comparative Example 5 C-5 11.0 20.2 55.2 66.4 85.1

Referring to Table 3, Examples (S-1) to (S-3) are Comparative Examples (C-1) to (C-4) when the same water / cement (W / C) and aggregate are used. It can be seen that the copolymers obtained in Examples (S-1) to (S-3) have a superior effect on the early strength and long-term strength in the concrete composition. have. In addition, it can be seen that as the content of the unsaturated amine compound increases, the early strength expression effect of the concrete composition is excellent. From the above result, the amine derivative which exists in the side chain of an unsaturated amine compound is a part which can confirm that it has a big effect on the early strength expression of a concrete composition.

On the other hand, in the case of Comparative Example 5 compared to Examples 1 to 3 as a copolymer prepared except the unsaturated amine compound (b), it can be seen that both the early strength and the long-term strength of the obtained concrete construction body is low. Therefore, it can be seen that the unsaturated amine-based compound (b) is included as one monomer of the copolymer of the present invention, thereby making it possible to express early strength during construction of the concrete composition. In addition, the long-term strength can also be seen that the case of using the concrete admixture of the copolymer prepared according to Examples 1 to 3 is superior to the case of using the copolymer of Comparative Example 5.

Through the total organic carbon analysis and concrete test of the copolymer, the copolymer for concrete admixtures prepared according to the examples (S-1) to (S-3) and the copolymer for concrete admixtures prepared according to the comparative example (C -1) to (C-4) are copolymers using unsaturated (meth) polyoxyalkylene urethane compounds and unsaturated organic acid compounds when used as concrete admixtures, compared with those using methoxypolyethylene glycol methacrylate and unsaturated organic acid compounds. It has been confirmed that it has a strong initial dispersing force and a dispersing retention over time, and also improves the workability of the concrete composition, and the copolymers polymerized with different amounts of the unsaturated amine compound have a higher initial content of the concrete composition as the content of the unsaturated amine compound increases. It can be seen that it promotes strength expression.

Accordingly, it is possible to provide a copolymer that can be used as an admixture for premature strength-expressing concrete capable of shortening the construction period and reducing raw material costs according to the early strength of the concrete composition.

Claims (14)

At least one unsaturated (meth) polyoxyalkylene urethane compound of formula (a), at least one unsaturated amine compound (b) of formula (2), and at least one unsaturated anionic organic compound of formula (3) copolymer of c):
Formula 1

(In Formula 1,
X ₁ , Y ₁ and Z ₁ are the same as or different from each other independently and are each hydrogen (-H), methyl group (-CH ₃ ) or carboxylic acid group (-COOH),
R ₁ is a hydrocarbon group or ketone group having 1 to 6 carbon atoms,
R ₂ is an aromatic group having 6 carbon atoms, a cyclic hydrocarbon group having 3 to 12 carbon atoms, or a hydrocarbon group having 1 to 6 carbon atoms,
R ₃ is hydrogen (-H) or a hydrocarbon group of 1 to 6 carbon atoms,
P _l is O, and the oxyalkylene groups and at least one 2 to 20 carbon atoms,
m is an integer of 2 to 100 as the mole number of the oxyalkylene group, n is an integer of 1 to 50 as the average number of moles of the repeating unit,
The average mole number (m * n + m) of the total oxyalkylene groups is an integer from 50 to 100.)
Formula 2

(In the formula (2)
X ₂ , Y ₂ and Z ₂ are the same as or different from each other independently and are each selected from the group consisting of hydrogen (—H), methyl group (—CH ₃ ), provided that any one of X ₂ , Y ₂ and Z ₂ is Hydrogen,
R ₄ is a hydrocarbon group or ketone group having 1 to 6 carbon atoms,
R ₅ is a hydrocarbon group of 1 to 6 carbon atoms; And
R ₆ , R ₇ are the same as or different from each other independently and are each selected from the group consisting of hydrogen (-H), hydroxyl (-OH), or an alkyl alcohol group having 1 to 6 carbon atoms.)
Formula 3

(In Chemical Formula 3,
X ₃ , Y ₃ and Z ₃ are the same or different independently from each other and are each selected from the group consisting of hydrogen (-H), methyl group (-CH ₃ ) and carboxylic acid group (-COOH), provided that X ₃ , Y _{One of 3} and Z ₃ is hydrogen; And
R ₈ represents a carboxylic acid group (-COOH) or a nitrile group (-CN).) The method of claim 1,
10 parts by weight to 60 parts by weight of the unsaturated (meth) polyoxyalkylene urethane compound of Formula 1, 5 parts by weight to 30 parts by weight of the unsaturated amine compound of Formula 2, and an unsaturated anion of Formula 3 A copolymer comprising 10 parts by weight to 40 parts by weight of the organic compound (c). The method of claim 1,
The copolymer has a weight average molecular weight (Mw) of 5,000 to 150,000. The method of claim 1,
In Formula 1, m is 6 to 50 will be a copolymer. The method of claim 1,
The unsaturated (meth) polyoxyalkylene urethane compound of Formula 1 is a copolymer prepared by adding an unsaturated organic acid and urethane derivative-polyoxyalkylene. The method of claim 1,
The unsaturated amine compound of Formula 2 is a copolymer prepared by adding an unsaturated organic acid and an amine derivative. The method of claim 1,
The unsaturated anionic organic compound of Formula 3 may be acrylic acid, methacrylic acid, maleic acid, itaconic acid, citraconic acid, fumaric acid; A copolymer selected from the group consisting of these monovalent metal salts, divalent metal salts, ammonium groups, organic amine groups and anhydrides thereof. At least one unsaturated (meth) polyoxyalkylene urethane compound of formula (a), at least one unsaturated amine compound (b) of formula (2), and at least one unsaturated anionic organic compound of formula (3) Concrete admixture comprising the copolymer of c):
Formula 1

(In Formula 1,
X ₁ , Y ₁ and Z ₁ are the same as or different from each other independently and are each hydrogen (-H), methyl group (-CH ₃ ) or carboxylic acid group (-COOH),
R ₁ is a hydrocarbon group or ketone group having 1 to 6 carbon atoms,
R ₂ is an aromatic group having 6 carbon atoms, a cyclic hydrocarbon group having 3 to 12 carbon atoms, or a hydrocarbon group having 1 to 6 carbon atoms,
R ₃ is hydrogen (-H) or a hydrocarbon group of 1 to 6 carbon atoms,
P _l is O, and the oxyalkylene groups and at least one 2 to 20 carbon atoms,
m is an integer of 2 to 100 as the mole number of the oxyalkylene group, n is an integer of 1 to 50 as the average number of moles of the repeating unit,
The average mole number (m * n + m) of the total oxyalkylene groups is an integer from 50 to 100.)
Formula 2

(In the formula (2)
X ₂ , Y ₂ and Z ₂ are the same or different independently from each other and are each selected from the group consisting of hydrogen (—H), methyl group (—CH ₃ ), provided that any one of X ₂ , Y ₂ and Z ₂ is Hydrogen,
R ₄ is a hydrocarbon group or ketone group having 1 to 6 carbon atoms,
R ₅ is a hydrocarbon group of 1 to 6 carbon atoms; And
R ₆ , R ₇ are the same as or different from each other independently and are each selected from the group consisting of hydrogen (-H), hydroxyl (-OH), or an alkyl alcohol group having 1 to 6 carbon atoms.)
Formula 3

(In Chemical Formula 3,
X ₃ , Y ₃ and Z ₃ are the same or different independently from each other and are each selected from the group consisting of hydrogen (-H), methyl group (-CH ₃ ) and carboxylic acid group (-COOH), provided that X ₃ , Y _{One of 3} and Z ₃ is hydrogen; And
R ₈ represents a carboxylic acid group (-COOH) or a nitrile group (-CN).) The method of claim 8,
10 parts by weight to 60 parts by weight of the unsaturated (meth) polyoxyalkylene urethane compound of Formula 1, 5 parts by weight to 30 parts by weight of the unsaturated amine compound of Formula 2, and an unsaturated anion of Formula 3 A concrete admixture comprising 10 parts by weight to 40 parts by weight of the organic compound (c). The method of claim 8,
Concrete copolymer having a weight average molecular weight (Mw) of 5,000 to 150,000. The method of claim 8,
In Formula 1, m is 6 to 50 concrete admixture. The method of claim 8,
The unsaturated (meth) polyoxyalkylene urethane compound of Formula 1 is prepared by adding an unsaturated organic acid and urethane derivative-polyoxyalkylene concrete admixture. The method of claim 8,
The unsaturated amine compound of Formula 2 is prepared by adding an unsaturated organic acid and an amine derivative concrete admixture. The method of claim 8,
The unsaturated anionic organic compound of Formula 3 may be acrylic acid, methacrylic acid, maleic acid, itaconic acid, citraconic acid, fumaric acid; Concrete admixture selected from the group consisting of monovalent metal salts, divalent metal salts, ammonium groups, organic amine groups and anhydrides thereof.

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