JP2010163325A - Dispersant composition for hydraulic composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a dispersant composition for a hydraulic composition excellent in dispersibility of a hydraulic powder such as cement, giving a hardened body of a hydraulic composition with high initial strength. <P>SOLUTION: This dispersant composition for a hydraulic composition contains a copolymer of an unsaturated carboxylic acid-based compound and an ester between a (meth)acrylic acid-based polymer and an alkoxypolyalkyleneglycol in which the average addition mole number (n<SB>A</SB>) of alkyleneoxide is 2-300; and an alkoxypolyalkyleneglycol in which the average addition number (n<SB>B</SB>) of alkyleneoxide is 2-300, at a specific weight ratio, where the ratio (n<SB>A</SB>)/(n<SB>B</SB>) of the average addition mole number is 0.9-1.1. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to a dispersant composition for a hydraulic composition and a method for producing the same.

  In order to impart fluidity to hydraulic compositions such as concrete, admixtures such as naphthalene-based, melamine-based, aminosulfonic acid-based, and polycarboxylic acid-based materials (high performance water reducing agents) are used. Conventionally, it has been proposed to use, as a polycarboxylic acid-based admixture, a polymer using a monomer having an alkoxypolyalkylene glycol structure as an admixture for a hydraulic composition. For admixtures such as water reducing agents, various performances are required such as imparting fluidity to hydraulic compositions, fluidity retention (flow retention), prevention of cure delay, etc. Improvements are also proposed from this perspective.

  Patent Document 1 discloses a cement admixture containing a specific molecular weight polyalkylene glycol (A) and a polyalkylene glycol mono (meth) acrylate / unsaturated carboxylic acid copolymer (B) in a specific weight ratio. The average molecular weight (X) of the polyalkylene glycol (A) and the average molecular weight (Y) of the polyalkylene glycol chain portion of the polyalkylene glycol mono (meth) acrylate / unsaturated carboxylic acid copolymer (B) are predetermined. A cement admixture that satisfies the relationship is described.

  Patent Document 2 describes a graft polymer having a specific structure that can be used as a water reducing agent for cement.

  Patent Document 3 discloses a polymer A prepared from a monomer containing a monomer a such as an unsaturated monocarboxylic acid, and one terminal is terminated with a terminal group that is not reactive under normal reaction conditions. It is described that a polymer in the solid state, obtained by reacting a hydroxyl-functionalized or amine-functionalized polymer B and optionally an amine C, can be used as a dispersant for hydraulic binders. ing.

JP 2002-12461 A, JP 2006-63303 A JP 2005-520900 Gazette

  The subject of this invention is providing the dispersing agent for hydraulic compositions which is excellent in the dispersibility of hydraulic powder, such as cement, and from which the hardening body of a hydraulic composition with high initial strength is obtained.

The present invention relates to a copolymer A containing a structural unit (A1) represented by the general formula (1) and a structural unit (A2) represented by the general formula (2), and an average added mole number of alkylene oxide (n _B ) is an alkoxy polyalkylene glycol having 2 to 300 (hereinafter referred to as ether compound B) in a weight ratio of ether compound B / copolymer A = 0.40 to 1.9. The ratio of the average added mole number of alkylene oxide (n _A ) in the general formula (1) to the average added mole number of alkylene oxide (n _B ) in the ether compound B is 0 (n _A ) / (n _B ). It is related with the dispersing agent composition for hydraulic compositions which is 9-1.1.

[Where,
R ¹¹ : hydrogen atom or methyl group, preferably hydrogen atom R ¹² : hydrogen atom, methyl group, or COOM, preferably hydrogen atom R ¹³ : hydrogen atom, methyl group, CH ₂ COOM, or COOM, preferably hydrogen atom or methyl X: oxyalkylene group having 2 to 8 carbon atoms, preferably an oxyalkylene group n _a 2 to 4 carbon atoms: average addition mole number 2 to 300 of X, preferably 5 to 200, more preferably 10 to 120
Y: C1-C18 alkyl group, preferably C1-C4 alkyl group M: Hydrogen atom, alkali metal, alkaline earth metal (1/2 atom), ammonium group, alkylammonium group, substituted alkylammonium Represents a group, an alkyl group, a hydroxyalkyl group or an alkenyl group, preferably a hydrogen atom, an alkali metal or an ammonium group. ]

[Where,
R ²¹ : hydrogen atom or methyl group, preferably hydrogen atom R ²² : hydrogen atom, methyl group, or COOM ′, preferably hydrogen atom R ²³ : hydrogen atom, methyl group, CH ₂ COOM ′, or COOM ′, preferably Hydrogen atom or methyl group M ′: hydrogen atom, alkali metal, alkaline earth metal (1/2 atom), ammonium group, alkylammonium group, substituted alkylammonium group, alkyl group, hydroxyalkyl group, or alkenyl group, preferably Represents a hydrogen atom, an alkali metal or an ammonium group. ]

Further, the present invention is a method for producing a dispersant composition for a hydraulic composition of the present invention,
Monomer containing a monomer (a2) represented by the following general formula (4) in a solvent containing an alkoxypolyalkylene glycol (hereinafter referred to as ether compound _A ) having an average addition mole number (n _A ) of alkylene oxide of 2 to 300 To obtain a carboxylic acid polymer containing at least the structural unit (A2),
And a step of obtaining a copolymer A by a (partial) esterification reaction of the carboxylic acid polymer obtained in the above step and the ether compound A, and the esterification reaction is carried out by using an unreacted ether compound A as an ether compound. B ends when present in the weight ratio with copolymer A,
The present invention relates to a method for producing a dispersant composition for a hydraulic composition.

[Where,
R ⁴¹ : hydrogen atom or methyl group, preferably hydrogen atom R ⁴² : hydrogen atom, methyl group, or COOM ⁴¹ , preferably hydrogen atom R ⁴³ : hydrogen atom, methyl group, CH ₂ COOM ⁴¹ , or COOM ⁴¹ , preferably Hydrogen atom or methyl group M ⁴¹ : hydrogen atom, alkali metal, alkaline earth metal (1/2 atom), ammonium group, alkylammonium group, substituted alkylammonium group, alkyl group, hydroxyalkyl group, or alkenyl group, preferably Represents a hydrogen atom, an alkali metal or an ammonium group. ]

Further, the present invention is a method for producing a dispersant composition for a hydraulic composition of the present invention,
An alkoxypolyalkylene glycol (hereinafter referred to as ether compound _A ) having an average added mole number (n _A ) of alkylene oxide of 2 to 300 is esterified with a carboxylic acid-based polymer containing at least the structural unit (A2). And a step of obtaining the polymer A, and the esterification reaction is terminated when the unreacted ether compound A is present as the ether compound B in the weight ratio with the copolymer A.
The present invention relates to a method for producing a dispersant composition for a hydraulic composition.

  ADVANTAGE OF THE INVENTION According to this invention, the dispersing agent for hydraulic compositions which is excellent in the dispersibility of hydraulic powders, such as cement, and can obtain the hardening body of a hydraulic composition with high initial strength is provided.

  Copolymer A includes, as structural units, (I) alkoxy polyalkylene glycol (ether compound A), structural unit (A1) derived from unsaturated carboxylic acid compound, and (II) unsaturated carboxylic acid compound. Derived structural unit (A2).

The ether compound A constituting the structural unit (A1) is a monoalkyl ether of polyalkylene glycol, and the polyalkylene glycol is preferably composed of an oxyalkylene group having 2 to 8 carbon atoms. The alkoxy group preferably has 1 to 18 carbon atoms, and more preferably 1 to 8 carbon atoms. The ether compound A has an average added mole number n _{A of} alkylene oxide of 2 to 300, preferably 5 to 200, more preferably 10 to 120.

  In addition, examples of the unsaturated carboxylic acid compound that is a monomer constituting the structural unit (A1) include acrylic acid, methacrylic acid, crotonic acid, maleic acid, itaconic acid, and citraconic acid. Acrylic acid and methacrylic acid are particularly preferred. It is preferable to contain acrylic acid and / or methacrylic acid. These monomers may be used alone or in combination of two or more.

  Although the weight average molecular weight of a structural unit (A1) can be determined in consideration of the weight average molecular weight of the copolymer A, 150-10000 are preferable.

  Examples of the unsaturated carboxylic acid compound which is a monomer constituting the structural unit (A2) include (I) unsaturated monocarboxylic acids such as acrylic acid, methacrylic acid, crotonic acid and their metal salts, ammonium salts and amine salts. Acid compounds, (II) maleic acid, itaconic acid, citraconic acid, fumaric acid, and unsaturated dicarboxylic acid compounds such as metal salts, ammonium salts, and amine salts thereof, (III) and maleic anhydride, itaconic anhydride And anhydrides of unsaturated dicarboxylic acid compounds such as citraconic anhydride. Among these, unsaturated monocarboxylic acid compounds are preferable, and acrylic acid, methacrylic acid and salts thereof are particularly preferable. These monomers may be used alone or in combination of two or more.

  The molar ratio of the structural unit (A1) to the total structural unit of the copolymer A [structural unit (A1) / total structural unit] is preferably 0.01 to 0.6, more preferably 0.05. It is -0.5, More preferably, it is 0.1-0.5.

  The molar ratio of the structural unit (A1) to the structural unit (A2) [structural unit (A1) / structural unit (A2)] is preferably 0.01 to 1.5, more preferably 0.05 to 1. More preferably, it is 0.1-1.

  The total molar ratio of the structural unit (A1) and the structural unit (A2) to the total structural units of the copolymer A [[structural unit (A1) + structural unit (A2)] / total structural unit] is 0. 0.5 to 1 is preferable, and 0.75 to 1 is more preferable.

  From the viewpoint of dispersibility of the hydraulic composition, the weight average molecular weight of the copolymer A is preferably 10,000 to 200,000, more preferably 20,000 to 100,000, and more preferably 30,000 to 80,000.

The ether compound B is also a monoalkyl ether of polyalkylene glycol, and the polyalkylene glycol is preferably composed of an oxyalkylene group having 2 to 8 carbon atoms. The alkoxy group preferably has 1 to 18 carbon atoms, and more preferably 1 to 4 carbon atoms. The ether compound B has an average added mole number n _{B of} alkylene oxide of 2 to 300, preferably 5 to 200, more preferably 9 to 130.

In the dispersant composition for a hydraulic composition of the present invention, from the viewpoint of productivity, the average number of added moles (n _A ) of alkylene oxide in the ether compound A in the copolymer A and the alkylene oxide in the ether compound B the ratio of the average addition molar number and (n _B) of a 0.9 to 1.1 with _{(n a) / (n B} ), 0.95~1.05 is preferred, within the above range If so, the same raw material is not necessarily required.

  In the dispersant composition for a hydraulic composition of the present invention, from the viewpoint of increasing the initial strength of the cured product of the hydraulic composition, the weight ratio of the copolymer A and the ether compound B is such that the ether compound B / copolymer. A is 0.40 to 1.9, 0.45 to 1.5 is preferable, and 0.50 to 1.0 is more preferable. In addition, the weight of the copolymer A is calculated in terms of an acid type in the case of a salt type.

  The dispersant composition for a hydraulic composition of the present invention preferably contains 34 to 71% by weight of copolymer A, more preferably 40 to 69% by weight, and further 50 to 67% by weight. Moreover, it is preferable to contain 29-66 weight% of ether compounds B, Furthermore, 31-60 weight%, Furthermore, 33-50 weight% is contained. In the dispersant composition for a hydraulic composition of the present invention, the total of the copolymer A and the ether compound B is preferably 10 to 100% by weight, more preferably 30 to 95% by weight.

The method for producing the dispersant composition for a hydraulic composition of the present invention is not particularly limited. For example, as described above, the monomer (a1) represented by the general formula (3) and the general formula (4) The copolymer (A2) is copolymerized to synthesize a copolymer A, and both components may be mixed so that the copolymer A and the ether compound B are in the weight ratio range ( Hereinafter, the method 1). In this case, the copolymer A and the polyalkylene glycol chain part of the ether compound B can be easily produced even if they do not have the same structure. Further, a copolymer using acid type monomers (M ³¹ and M ⁴¹ are hydrogen atoms) as the monomer (a1) represented by the general formula (3) and the monomer (a2) represented by the general formula (4) A may be synthesized and used without being neutralized, or it may be partially or completely neutralized with a base.

[Where,
R ³¹ : hydrogen atom or methyl group R ³² : hydrogen atom, methyl group, or COOM ³¹
R ³³ : hydrogen atom, methyl group, CH ₂ COOM ³¹ , or COOM ³¹
X ³¹ : oxyalkylene group having 2 to 8 carbon atoms n _3A : average added mole number of X ³¹ 2 to 300
Y ³¹ : alkyl group having 1 to 18 carbon atoms M ³¹ : hydrogen atom, alkali metal, alkaline earth metal (1/2 atom), ammonium group, alkylammonium group, substituted alkylammonium group, alkyl group, hydroxyalkyl group, Or represents an alkenyl group. ]

[Where,
R ⁴¹ : hydrogen atom or methyl group R ⁴² : hydrogen atom, methyl group, or COOM ⁴¹
R ⁴³ : hydrogen atom, methyl group, CH ₂ COOM ⁴¹ , or COOM ⁴¹
M ^{41 represents a} hydrogen atom, an alkali metal, an alkaline earth metal (1/2 atom), an ammonium group, an alkyl ammonium group, a substituted alkyl ammonium group, an alkyl group, a hydroxyalkyl group, or an alkenyl group. ]

  Specific examples and preferred compounds of the monomer (a1) are the same as the monomers constituting the structural unit (A1) described above. Specific examples and preferred compounds of the monomer (a2) are the same as the monomer constituting the structural unit (A2).

  As another production method of the dispersant composition for hydraulic composition of the present invention, when producing monomer (a1) by esterification reaction of monomer (a2) and ether compound A, the esterification reaction is stopped halfway. , Leaving the unreacted monomer (a2), polymerizing the monomer (a2) and the produced monomer (a1) to produce a copolymer A and leaving the ether compound A as the ether compound B (hereinafter, Method 2-1). This method is to obtain the dispersant composition for a hydraulic composition of the present invention containing the copolymer A and the ether compound B as a reaction product (mixture) obtained in the monomer production process. This method comprises a step (esterification step) of obtaining a reaction product comprising an ester of an ether compound A and a monomer (a2) [namely, the monomer (a1)], an unreacted monomer (a2) and the ether compound A; A hydraulic composition comprising: a step of producing a copolymer A by reacting the ester [that is, the monomer (a1)] and the unreacted monomer (a2) in the presence of the unreacted ether compound A; This is a production method of a physical dispersant composition, and ends when unreacted ether compound A is present as ether compound B in the esterification step in the weight ratio. Specifically, for example, when an esterification reaction is carried out using ether compound A and an unsaturated carboxylic acid compound, the reaction is stopped under the condition that unreacted polyalkylene glycol and unsaturated carboxylic acid compound remain. Thereafter, a polymerization reaction is performed with the unreacted polyalkylene glycol remaining as the ether compound B to synthesize the copolymer A, and the weight ratio of the copolymer A and the ether compound B falls within the above weight ratio range. Can be. Further, the ether compound B may be further added later and adjusted so that the weight ratio of the copolymer A and the ether compound B falls within the above range.

As a method for obtaining a dispersant composition for a hydraulic composition of the present invention, a step of polymerizing a monomer (a2) in a solvent containing an ether compound A to obtain a carboxylic acid polymer containing at least a structural unit (A2) When,
And a step of obtaining a copolymer A by a (partial) esterification reaction of the carboxylic acid polymer obtained in the above step and the ether compound A, and the esterification reaction is carried out by using an unreacted ether compound A as an ether compound. B ends when present in the weight ratio with copolymer A,
The manufacturing method (henceforth method 2-2) of the dispersing agent composition for hydraulic compositions is mentioned. Further, the ether compound B may be further added later and adjusted so that the weight ratio of the copolymer A and the ether compound B falls within the above range.

  As yet another method for producing the cement admixture of the present invention, when a polymer is obtained by esterification of a carboxylic acid-based polymer containing the ether compound A and at least the structural unit (A2), the esterification reaction is stopped in the middle. Examples thereof include a method in which compound A remains as ether compound B (hereinafter referred to as method 2-3). This method comprises a step of esterifying an ether compound A and an unsaturated carboxylic acid polymer containing at least the structural unit (A2) to obtain a copolymer A, and the esterification reaction is unreacted. This is a method for producing a dispersant composition for a hydraulic composition, which is completed when the ether compound A is present as the ether compound B in the weight ratio with the copolymer A. Specifically, for example, at least a part of the carboxyl group of the carboxylic acid polymer containing at least the structural unit (A2) obtained by polymerizing the monomer containing the monomer (a2) is directly esterified with the ether compound A. The copolymer A is synthesized by a so-called “polymer post-esterification reaction”, and the esterification reaction is stopped so that the weight ratio of the copolymer A and the remaining ether compound A is within the above weight ratio range. It may be. In this case, the ether compound B may be further added later and adjusted so that the weight ratio of the copolymer A and the ether compound B falls within the above range.

  As in Method 2-2, the monomer containing the monomer (a2) is polymerized in a solvent containing the ether compound A under conditions without esterification, an esterification catalyst is added to the mixture, and esterification is performed. The effective amount is high, which is preferable from the viewpoint of improving productivity and suppressing energy costs. The water produced by the esterification reaction may be distilled out of the reaction system, but in order to actively increase the residual amount of the ether compound B, the reaction rate should not be distilled out of the system. It is preferable from the viewpoint of control.

  In Method 2-2, the reaction temperature when the monomer containing the monomer (a2) is polymerized in the solvent containing the ether compound A is preferably 50 to 200 ° C, more preferably 70 to 100 ° C. In the reaction, it is preferable to use a polymerization initiator or a chain transfer agent.

  As an aqueous polymerization initiator, persulfuric acid ammonium salt or alkali metal salt or hydrogen peroxide, 2,2′-azobis (2-amidinopropane) dihydrochloride, 2,2′-azobis (2-methylpropionamide) Water-soluble azo compounds such as dihydrate are used. For solution polymerization using a non-aqueous solvent, peroxides such as benzoyl peroxide and lauroyl peroxide, aliphatic azo compounds such as azobisisobutyronitrile, and the like are used. Moreover, accelerators, such as sodium hydrogen sulfite and an amine compound, can also be used in combination with a polymerization initiator. Although superposition | polymerization temperature is suitably determined with the solvent and polymerization initiator to be used, it is 0-120 degreeC normally, and 30 degreeC or more is preferable. More preferably, it is 50 ° C. or higher. Moreover, 100 degrees C or less is preferable. More preferably, it is 95 degrees C or less. It is preferable to use it at a ratio of 0.01 to 20 mol% with respect to the unsaturated carboxylic acid compound. Chain transfer agents include mercaptoethanol, thioglycerol, thioglycolic acid, 2-mercaptopropionic acid, 3-mercaptopropionic acid, thiomalic acid, octyl thioglycolate, octyl 3-mercaptopropionate, 2-mercaptoethanesulfonic acid, thiol chain transfer agents such as n-dodecyl mercaptan, octyl mercaptan, butyl thioglycolate; halides such as carbon tetrachloride and methylene chloride; secondary alcohols such as isopropanol; phosphorous acid, hypophosphorous acid, sulfurous acid, Examples thereof include hydrogen sulfite, dithionite, metabisulfite, and salts thereof, and it is preferably used at a ratio of 0.1 to 10 mol% with respect to the unsaturated carboxylic acid compound. Moreover, although reaction time is based also on the residual amount of the ether compound B, etc., it is 0.5 to 12 hours, Furthermore, 1.5 to 6 hours are preferable.

  In the methods 2-2 and 2-3, the reaction temperature when esterifying the ether compound A and the carboxylic acid polymer containing at least the structural unit (A2) is 80 to 200 ° C., more preferably 100 to 150 ° C. . In the reaction, it is preferable to use an esterification catalyst, especially an acid catalyst. Examples of the acid catalyst include p-toluenesulfonic acid, p-toluenesulfonic acid monohydrate, m-xylenesulfonic acid, methanesulfonic acid, sulfuric acid, phosphoric acid, hydrochloric acid, and the like. It is preferably used at a ratio of 0.1 to 100 mol, more preferably 0.5 to 50 mol, and further preferably 1 to 30 mol. Moreover, although reaction time is based also on the residual amount of the ether compound B, 2 to 24 hours, and also 5 to 18 hours are preferable. The progress and termination of the esterification reaction are based on the fact that the copolymer A is produced at a predetermined esterification rate by measuring the acid value of the reaction system, structural analysis by NMR, etc., and that the copolymer A and the ether compound B are It can be determined by confirming that the predetermined weight ratio is obtained.

  In the methods 2-2 and 2-3, as the charging ratio for the copolymer A to have a predetermined esterification rate and the weight ratio of the copolymer A and the ether compound B in the dispersant composition to be in a predetermined range Is preferably a weight ratio of ether compound A / carboxylic acid polymer containing at least the structural unit (A2) = 2/1 to 100/1, more preferably 4/1 to 50/1, and 8/1 to 25/1. Is more preferable. In order to adjust the weight ratio of copolymer A and ether compound B, copolymer A and / or ether compound B may be added later.

  In addition to copolymer A and ether compound B, the dispersant composition for hydraulic composition of the present invention includes conventional cement dispersant, water-soluble polymer, air entraining agent, cement wetting agent, expansion agent, waterproofing agent. , Retarders, quick setting agents, water-soluble polymer substances, thickeners, flocculants, drying shrinkage reducers, strength enhancers, curing accelerators, and the like may be used in combination.

  The present invention provides a hydraulic composition comprising the dispersant composition for a hydraulic composition of the present invention, a hydraulic powder, and water.

  The hydraulic powder is a powder having physical properties that are cured by a hydration reaction, and examples thereof include cement and gypsum. Cement is preferable, and ordinary cements such as Portland cement, Belite cement, medium heat cement, early strong cement, super early strong cement, sulfuric acid resistant cement, etc., and blast furnace slag, fly ash, silica fume, stone powder ( It may be added with calcium carbonate powder). In addition, early strong cement, super early strong cement, high belite cement, eco-cement, etc. may be used. In addition, the hydraulic composition finally obtained by adding sand, sand and gravel as aggregates to these powders is generally called mortar, concrete, etc., respectively. The admixture of the present invention is not only for ready-mixed concrete and concrete vibration products, but also for self-leveling, for refractories, for plaster, for gypsum slurry, for lightweight or heavy concrete, for AE, for repair, for prepacked, for trayy, It is useful in any field of various concrete such as grout, ground improvement, and cold.

  As the water, those usually used can be used, and examples thereof include tap water.

  The hydraulic composition of the present invention has a water / hydraulic powder ratio (W / P) of 65% or less, further 10 to 60%, further 12 to 57%, further 15 to 55%, particularly 20 to 55%. Can be. W / P is calculated by weight percentage (% by weight) of water (W) and hydraulic powder (P) in the hydraulic composition, that is, (W / P) × 100.

  Moreover, the hydraulic composition of this invention can contain an aggregate. Examples of the aggregate include fine aggregate (S) and coarse aggregate (G). Examples of the fine aggregate (S) include those defined in JIS A0203-2302.

  Fine aggregates include rivers, land, mountains, sea, lime sand, quartz sand and crushed sand, blast furnace slag fine aggregates, ferronickel slag fine aggregates, lightweight fine aggregates (artificial and natural) and recycled fine aggregates. Etc.

  Moreover, what is prescribed | regulated by JIS A0203-2303 is mentioned as a coarse aggregate (G). For example, as coarse aggregate, river, land, mountain, sea, lime gravel, crushed stone, blast furnace slag coarse aggregate, ferronickel slag coarse aggregate, lightweight coarse aggregate (artificial and natural), recycled coarse aggregate, etc. Is mentioned.

  In the hydraulic composition of the present invention, the dispersant composition of the present invention is used in a proportion of 0.01 to 10 parts by weight, and further 0.05 to 3 parts by weight with respect to 100 parts by weight of the hydraulic powder. Is preferred.

  Further, in the hydraulic composition of the present invention, the dispersant composition of the present invention is such that the copolymer A is 0.01 to 100 parts by weight of the hydraulic powder from the viewpoint of fluidity of the hydraulic composition. It is preferably used so as to have a ratio of 1 part by weight, further 0.05 to 0.5 part by weight, and further 0.08 to 0.3 part by weight.

  Further, in the hydraulic composition of the present invention, the dispersant composition of the present invention is a hydraulic powder in which the total of copolymer A and ether compound B is from the viewpoint of fluidity and initial strength expression of the hydraulic composition. It is preferably used in a ratio of 0.02 to 1.5 parts by weight, further 0.08 to 1.0 parts by weight, and further 0.1 to 0.4 parts by weight with respect to 100 parts by weight.

  The hydraulic composition of the present invention includes, in addition to the dispersant composition of the present invention, hydraulic powder, and water, a conventional cement dispersant, a water-soluble polymer, an air entraining agent, a cement wetting agent, an expanding material, and waterproofing. Agents, retarders, quick setting agents, water-soluble polymer substances, thickeners, flocculants, drying shrinkage reducers, strength enhancers, curing accelerators and the like may be used in combination.

Production Example 1 (Production of copolymer P-2)
A glass reaction vessel equipped with a thermometer, a stirrer, a dropping funnel, a nitrogen inlet tube and a reflux condenser was charged with 1887 g of water, the inside of the reaction vessel was purged with nitrogen under stirring, and the temperature was raised to 78 ° C. under a nitrogen atmosphere. Next, (1) a monomer solution in which 2500 g of methoxypolyethylene glycol monoacrylate (average added mole number of ethylene oxide: 23% 65% aqueous solution) and (2) 320 g of acrylic acid were mixed and dissolved, and 14 g of 3-mercaptopropionic acid were added to water. An aqueous solution dissolved in 56 g and (3) an aqueous solution in which 13.5 g of ammonium persulfate was dissolved in 100 g of water were each dropped with a dropping funnel over 1.5 hours. After completion of the dropwise addition, an aqueous solution obtained by further dissolving 6.8 g of ammonium persulfate in 50 g of water was further added dropwise over 0.5 hours. Thereafter, aging was further carried out at 78 ° C. for 1 hour to complete the polymerization reaction. The aqueous solution containing the obtained reaction product was neutralized with a 48% aqueous sodium hydroxide solution to obtain an aqueous solution of copolymer P-2 having a pH of 6.2 and a weight average molecular weight of 40000.

  Other copolymers P-1, P-3, and P-4 were also obtained by polymerization in the same procedure with the monomer species and composition changed as shown in Table 2.

Production Example 2 (Production of mixture containing copolymer P-7)
(2-1)
Production of methoxypolyethylene glycol solution of polyacrylic acid A glass reaction vessel equipped with a thermometer, stirrer, nitrogen inlet tube and condenser for distillation was charged with 423 g of methoxypolyethylene glycol (average added mole number of ethylene oxide 23) and stirred. The inside of the reaction vessel was replaced with nitrogen below, and the temperature was raised to 78 ° C. in a nitrogen atmosphere. A solution in which 72.1 g of acrylic acid, 72.1 g of methoxypolyethylene glycol, 3.0 g of 3-mercaptopropionic acid and 2.85 g of azobisisobutyronitrile were dissolved was dropped with a dropping funnel over 1.0 hour. After completion of the dropwise addition, aging was further performed at 78 ° C. for 2 hours to obtain a methoxypolyethylene glycol solution (A-1) of polyacrylic acid having a number average molecular weight of 26000.

(2-2) Production of acrylic acid / methoxypolyethylene glycol acrylate copolymer In a glass reaction vessel equipped with a thermometer, a stirrer, a nitrogen inlet tube and a condenser for distillation, a methoxypolyethylene glycol solution of polyacrylic acid (A- 1) (Complete acid type unneutralized product) 200 g and p-toluenesulfonic acid monohydrate (PTS) 1.8 g were charged, the inside of the reaction vessel was purged with nitrogen, heated to 80 ° C. in a nitrogen atmosphere, and stirred. To uniformly dissolve the contents. Thereafter, the temperature was raised to 120 ° C. while blowing nitrogen into the reaction vessel, and the esterification reaction was continued while maintaining the generated water at 120 ° C. without distilling out of the system. The reaction was traced by taking out a part of the reaction product every 30 minutes from the time when the temperature reached 100 ° C. and measuring the acid value. When the esterified carboxyl group amount is 25%, that is, when the reaction rate of methoxypolyethylene glycol is 53%, the temperature is lowered to complete the esterification reaction, and after cooling, water is added, and 48% aqueous sodium hydroxide solution is added. Neutralization gave a mixture containing acrylic acid / methoxypolyethylene glycol acrylate copolymer P-7 having an average molecular weight of 31400 and methoxypolyethylene glycol. The weight ratio (ether compound B / copolymer A) is 0.71, the average added mole number of alkylene oxide in copolymer A (n _A ) is 23, and the average added mole number of alkylene oxide in ether compound B. (N _B ) is 23, and the ratio (n _A ) / (n _B ) of the average added mole number is 1.0.

  The weights of the copolymer A and the ether compound B were calculated from the amount of esterified carboxyl groups after completion of the esterification reaction and the weights of polyacrylic acid and methoxypolyethylene glycol used for the synthesis.

The amount of the esterified carboxyl group was calculated from the decrease in proton intensity adjacent to the hydroxyl group based on the result of ¹ H-NMR under the following conditions.
^[1 H-NMR measurement conditions]
Device: Varian Mercury 400 (400 MHz)
Pulse sequence: North pin, 10Hz
Pulse width: 45 °
Measurement temperature: 20 ° C
Pulse delay time: 10 sec
Integration count: 32 observations Data points: 64000
Solvent: CDCl ₃ (deuterated chloroform) (2% by weight)

  The mixture containing other copolymer P-5 and the mixture containing P-6 were also obtained by polymerizing in the same procedure with the monomer species and composition changed as shown in Table 2.

Production Example 3 (Production of mixture containing copolymer P-9)
(3-1) Production of polyacrylic acid aqueous solution 104 g of water was charged into a glass reaction vessel equipped with a thermometer, a stirrer, a nitrogen inlet tube and a condenser for distillation, and the inside of the reaction vessel was purged with nitrogen under stirring. The temperature was raised to 78 ° C. under an atmosphere. (1) 250% 80% acrylic acid aqueous solution, (2) an aqueous solution in which 7.4 g of 3-mercaptopropionic acid is dissolved in 16 g of water, and (3) an aqueous solution in which 3.2 g of ammonium persulfate is dissolved in 12 g of water. Were added dropwise with a dropping funnel over 1.5 hours. Thereafter, an aqueous solution obtained by further dissolving 1.6 g of ammonium persulfate in 5.9 g of water was added dropwise over 0.5 hours. After completion of the dropwise addition, the mixture was further aged at 78 ° C. for 1 hour to obtain a polyacrylic acid aqueous solution (A-2) having a number average molecular weight of 36000.

(3-2) Production of acrylic acid / methoxypolyethylene glycol acrylate copolymer (polymer partial esterification)
In a glass reaction vessel equipped with a thermometer, a stirrer, a nitrogen inlet tube and a condenser for distillation, 144 g of polyacrylic acid (A-2) (completely neutralized non-neutralized product), methoxypolyethylene glycol (ethylene) (Oxide mole number 23 moles) 413g) and paratoluenesulfonic acid monohydrate (PTS) 5.0g were charged, the inside of the reaction vessel was purged with nitrogen, heated to 80 ° C under nitrogen atmosphere, and the contents were stirred. It was dissolved uniformly. Thereafter, the temperature was raised to 120 ° C. while blowing nitrogen into the reaction vessel, and the esterification reaction was continued while maintaining the temperature at 120 ° C. while distilling the produced water out of the system. The reaction was traced by taking out a part of the reaction product every 30 minutes from the time of reaching 100 ° C. and measuring the acid value. When the amount of esterified carboxyl groups was 25%, that is, the reaction rate of methoxypolyethylene glycol was 63%, the temperature was lowered to finish the esterification reaction, and after cooling, water was added, and 48% sodium hydroxide aqueous solution was used. Neutralization gave a mixture containing acrylic acid / methoxypolyethylene glycol acrylate copolymer P-9 having an average molecular weight of 49,500 and methoxypolyethylene glycol. The weight ratio of the copolymer P-9 (copolymer A) and methoxypolyethylene glycol (ether compound B) in the mixture (ether compound B / copolymer A) is 0.46. The average added mole number (n _A ) of the alkylene oxide is 23, and the average added mole number (n _B ) of the alkylene oxide in the ether compound _B is 23.

  The weight of copolymer A and ether compound B in the mixture was calculated from the amount of esterified carboxyl groups after completion of the esterification reaction and the weight of polyacrylic acid and methoxypolyethylene glycol used in the synthesis.

  The mixture containing other copolymer P-8 was also obtained by polymerizing in the same procedure with the monomer species and composition changed as shown in Table 3.

  Table 1 below shows the monomer type, composition, molecular weight and the like of the constituent units of the copolymer. Table 2 shows the ether compounds (ether compound A or ether compound B). Tables 3 and 4 below show the monomer type, composition, molecular weight and the like of the constituent units of the copolymer and the composition of the mixture. The copolymer of Table 1 and the ether compound of Table 2 were combined, or the mixture of Tables 3 and 4 was used as the dispersant composition.

Example (mortar test)
(1) Mortar combination

The components in the table are as follows.
C: Ordinary Portland cement (manufactured by Taiheiyo Cement Co., Ltd.) (density 3.16 g / cm ³ )
S: Fine aggregate, Joyosan sand (density 2.57 g / cm ³ )
W: Wakayama City tap water

(2) Manufacture of mortar Cement (C) and sand (S) were mixed and mixed at a low speed for 10 seconds using a mortar mixer in the formulation shown in Table 5, and water added with a dispersant composition and an ester-based antifoaming agent ( W) was added, and the mixture was further stirred and mixed at low speed for 2 minutes to produce a mortar. The production was carried out at 22 ° C. The ester antifoaming agent was used to remove the influence of entrained air, and was added to water (W) so that the amount was 0.04 g per kg of mortar.

(3) Mortar test The mortar flow of the mortar obtained above was measured according to JIS R 5201 (however, no drop motion was added), and a specimen having a diameter of 5 cm and a height of 10 cm was prepared. Cured at ℃. The initial strength of the cured mortar that was demolded after 24 hours was measured with a compressive strength tester. The results are shown in Tables 6-10.

The amount of the dispersant composition added is 100 parts by weight of cement (hereinafter the same). N _A / n _B is the ratio of the average number of added moles (n _A ) in the general formula (1) in the copolymer A to the average number of added moles (n _B ) in the ether compound B (n _A / n _B (The same applies hereinafter).

  In Tables 6-9, in order to make the mortar flow constant, the addition amount of the copolymer A was made constant, and the addition amount of the ether compound B was changed to change the B / A weight ratio.

In Table 6, Example 1-5 to which 0.24 parts by weight of ether compound B is added has an initial strength of 17.7 N / mm ² , and 17.0 N of Comparative Example 1-1 to which no ether compound B is added. The initial strength is about 4% higher than / mm ² . On the other hand, in Comparative Example 2-4 in Table 7, even if the amount of ether compound B added is the same as in Example 1-5, the initial strength is improved by only about 1% compared to Comparative Example 2-1 in which no ether compound is added. Not done. The same applies to Comparative Example 3-4 and Comparative Example 3-1 in Table 8. Therefore, it is considered that the effect of improving the initial strength is not simply the addition amount of the ether compound B but the B / A weight ratio is closer to the essence.

Claims (5)

The copolymer A containing the structural unit (A1) represented by the general formula (1) and the structural unit (A2) represented by the general formula (2), and the average added mole number (n _B ) of the alkylene oxide 2 to 300 alkoxy polyalkylene glycol (hereinafter referred to as ether compound B) in a weight ratio of ether compound B / copolymer A = 0.40 to 1.9. The ratio of the average number of moles of alkylene oxide (n _A ) in 1) to the average number of moles of alkylene oxide added (n _B ) in ether compound B is 0.9 to 1 in terms of (n _A ) / (n _B ) 1. Dispersant composition for hydraulic composition.

1 [where,
R ¹¹ : hydrogen atom or methyl group R ¹² : hydrogen atom, methyl group, or COOM
R ¹³ : hydrogen atom, methyl group, CH ₂ COOM, or COOM
X: oxyalkylene group having 2 to 8 carbon atoms n _A : average added mole number of X being 2 to 300
Y: alkyl group having 1 to 18 carbon atoms M: hydrogen atom, alkali metal, alkaline earth metal (1/2 atom), ammonium group, alkylammonium group, substituted alkylammonium group, alkyl group, hydroxyalkyl group, or alkenyl Represents a group. ]

[Where,
R ²¹ : hydrogen atom or methyl group R ²² : hydrogen atom, methyl group, or COOM ′
R ²³ : hydrogen atom, methyl group, CH ₂ COOM ′, or COOM ′
M ′ represents a hydrogen atom, an alkali metal, an alkaline earth metal (1/2 atom), an ammonium group, an alkylammonium group, a substituted alkylammonium group, an alkyl group, a hydroxyalkyl group, or an alkenyl group. ]   2. The hydraulic composition according to claim 1, wherein the molar ratio of the structural unit (A1) to the total structural unit of the copolymer A [structural unit (A1) / total structural unit] is 0.01 to 0.6. Dispersant composition.   The hydraulic composition containing the dispersing agent composition for hydraulic compositions of Claim 1 or 2, hydraulic powder, and water. A method for producing a dispersant composition for a hydraulic composition according to claim 1 or 2,
Monomer containing a monomer (a2) represented by the following general formula (4) in a solvent containing an alkoxypolyalkylene glycol (hereinafter referred to as ether compound _A ) having an average addition mole number (n _A ) of alkylene oxide of 2 to 300 To obtain a carboxylic acid polymer containing at least the structural unit (A2),
And a step of obtaining a copolymer A by a (partial) esterification reaction of the carboxylic acid polymer obtained in the above step and the ether compound A, and the esterification reaction is carried out by using an unreacted ether compound A as an ether compound. B ends when present in the weight ratio with copolymer A,
A method for producing a dispersant composition for a hydraulic composition.

[Where,
R ⁴¹ : hydrogen atom or methyl group R ⁴² : hydrogen atom, methyl group, or COOM ⁴¹
R ⁴³ : hydrogen atom, methyl group, CH ₂ COOM ⁴¹ , or COOz
M ^{41 represents a} hydrogen atom, an alkali metal, an alkaline earth metal (1/2 atom), an ammonium group, an alkyl ammonium group, a substituted alkyl ammonium group, an alkyl group, a hydroxyalkyl group, or an alkenyl group. ] A method for producing a dispersant composition for a hydraulic composition according to claim 1 or 2,
An alkoxypolyalkylene glycol (hereinafter referred to as ether compound _A ) having an average added mole number (n _A ) of alkylene oxide of 2 to 300 is esterified with a carboxylic acid-based polymer containing at least the structural unit (A2). And a step of obtaining the polymer A, and the esterification reaction is terminated when the unreacted ether compound A is present as the ether compound B in the weight ratio with the copolymer A.
A method for producing a dispersant composition for a hydraulic composition.