JP2001322853A - Dispersant for blast-furnace slag fine aggregate - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a dispersant for blast-furnace slag fine aggregate, by the use of which segregation of water or gravel in a hydraulic composition containing blast-furnace slag fine aggregate can be inhibited from being caused and workability of the hydraulic composition can be improved. SOLUTION: This dispersant contains a polymer which contains polyoxyalkylene groups having an average degree of condensation of oxyalkylene groups of 2-300.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a dispersant for blast furnace slag fine aggregate which facilitates operations such as driving, compaction and finishing of a hydraulic composition containing blast furnace slag fine aggregate and has excellent workability.

[0002]

BACKGROUND OF THE INVENTION Blast-furnace slag is used for mixed cement (JIS-5221 blast-furnace cement) because it is potentially hydraulically hard, but is mostly used as fine aggregate. Not. That is, when the blast furnace slag is mixed with a hydraulic composition because its surface is vitreous, the uniformity of the concrete is reduced because the water retention capacity is insufficient and the separation of water (breathing) and the separation of gravel as coarse aggregate become remarkable. Extremely poor, impairing workability such as driving.

[0003] The present invention relates to a hydraulic composition using blast furnace slag fine aggregate, which is useful as an admixture for hydraulic compositions, capable of suppressing material separation of water and gravel and improving workability. It is intended to provide a dispersant for aggregate.

[0004]

The present invention relates to a polyoxyalkylene group [average degree of condensation of oxyalkylene group (hereinafter referred to as n).
And a dispersant for blast-furnace slag fine aggregate containing a polymer containing

[0005] The present invention also relates to a hydraulic composition comprising a blast furnace slag fine aggregate, a hydraulic material, and the dispersant of the present invention.

[0006]

BEST MODE FOR CARRYING OUT THE INVENTION The polymer of the present invention includes a copolymer of a polyoxyalkylene (n = 2 to 300) alkenyl (C2 to C6) ether and maleic anhydride, and a copolymer of C2 to C3. One of the vinyl monomers (a) containing an oxyalkylene group at n = 2 to 300, preferably 100 to 200
A water-soluble copolymer (hereinafter, referred to as a water-soluble copolymer) obtained by polymerizing a monomer mixture containing at least one kind and at least one kind of a vinyl monomer (b) having a carboxyl group, a sulfonic acid group or an amide group. And the latter water-soluble copolymer is particularly preferred.

In the vinyl monomer (a) used for the above water-soluble copolymer, the oxyalkylene group having 2 to 3 carbon atoms is an oxyethylene group or an oxypropylene group. Either may be used. When both groups are present, the arrangement of these groups may be either block-like or random. As the monomer (a), a compound represented by the following general formula (A) is preferable.

[0008]

Embedded image

Wherein R ₁ and R ₂ are each a hydrogen atom or a methyl group, m1 is a number of 0 to 2, AO is an oxyalkylene group having 2 to 3 carbon atoms, n is a number of 2 to 300, and X is It represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and the n AOs may be the same or different. ].

The monomers represented by the general formula (A) include:
Methoxy polyethylene glycol, methoxy polyethylene polypropylene glycol, ethoxy polyethylene glycol, ethoxy polyethylene polypropylene glycol, propoxy polyethylene glycol, propoxy polyethylene polypropylene glycol and the like at one end alkyl group-blocked polyalkylene glycol and an ester compound of acrylic acid or methacrylic acid or acrylic acid or Ethylene oxide and propylene oxide adducts to methacrylic acid are used. n is the average number of moles added, and is 2 to 300, preferably 100 to 200, from the viewpoint of suppressing the breathing of concrete. In the present invention, a plurality of monomers in which n in the general formula (A) is different, for example, n is 100
~ 200 monomers and n ~ 2-50 monomers can be used.

The monomer (b) used in the above water-soluble copolymer is a vinyl monomer having a carboxyl group, a sulfonic acid group or an amide group, and is represented by the following general formula (B) or (B). Compounds represented by C) are preferred.

[0012]

Embedded image

Wherein R ₃ , R ₄ and R ₅ are each a hydrogen atom, a methyl group or — (CH ₂ ) _m2 COOM ₂ , R ₆ is a hydrogen atom or a methyl group, and M ₁ , M ₂ and Y are each A hydrogen atom or a cation group derived from metals such as sodium, potassium, calcium, and magnesium, ammonia, triethanolamine, diethanolamine, monoethanolamine, and the like, and m2 represents a number of 0 to 2. ].

The monomer represented by the general formula (B) includes
Acrylic acid, methacrylic acid, crotonic acid and metal salts thereof are mentioned. Examples of unsaturated dicarboxylic acid monomers include maleic anhydride, maleic acid, itaconic anhydride, itaconic acid, citraconic anhydride, citraconic acid, fumaric acid, or alkali metal salts, alkaline earth metal salts, and ammonium salts thereof. Salts, alkanolamine salts and the like, and monomers represented by the general formula (C) include allylsulfonic acid, methallylsulfonic acid, or alkali metal salts, alkaline earth metal salts, ammonium salts, and alkanols thereof. Amine salts and the like.

The water-soluble copolymer according to the present invention can be produced by a known method. For example, Japanese Unexamined Patent Publication No.
No. 62163, JP-A-62-70250, JP-A-62-78137, JP-A-7-223852
And the like. That is, it can be produced by polymerizing the above monomers (A), (B) and (C) in a suitable solvent. For example, in water or a lower alcohol having 1 to 4 carbon atoms, ammonium persulfate, in the presence of a polymerization initiator such as hydrogen peroxide, if necessary, add sodium hydrogen sulfite or mercaptoethanol, and the like at 50 to 100 ° C under a nitrogen atmosphere. The reaction may be performed for 0.5 to 10 hours. Note that other copolymerizable monomers such as acrylonitrile, acrylamide, methacrylamide, and styrene may be copolymerized as long as the effects of the present invention are not impaired.

In the monomer mixture for producing the water-soluble copolymer, the molar ratio of the monomers (a) and (b) is such that the monomer (a) / monomer (B) = 0.1 / 10
When the ratio is 0 to 200/100, the state of concrete viscosity (suppression of breathing and suppression of material separation) is excellent, and monomer (a) / monomer (b) = 10/100 to 100/10
A range of 0 (molar ratio) is particularly excellent.

The weight average molecular weight of the polymer of the present invention is 5,
The range of 000 to 100,000 is particularly excellent.

The dispersant of the present invention is added so that the ratio of the solid content of the polymer to the hydraulic material is 0.01 to 1.0% by weight, particularly 0.05 to 0.5% by weight. Is preferred.

The dispersant of the present invention may contain oxycarboxylic acid or a salt thereof, or a saccharide. Examples of oxycarboxylic acids or salts thereof include gluconic acid, glucoheptoic acid, arabic acid, malic acid, and citric acid; examples of these salts include, for example, inorganic salts such as sodium, potassium, calcium, magnesium, ammonium, and triethanol; Salts. As the saccharides, glucose, fructose, galactose, saccharose, xylose, abitose, ribose, maltose, monosaccharides such as isomerized sugar, disaccharides, oligosaccharides such as trisaccharides,
Or polysaccharides such as dextran. Also, molasses containing these are included. Further, examples of the sugar alcohol include sorbitol.

The dispersant of the present invention comprises a polymer containing a polyoxyalkylene group in an amount of 50 to 100% by weight, more preferably 80 to 10% by weight.
It is preferably contained at 0% by weight.

The hydraulic composition of the present invention contains blast furnace slag fine aggregate, a hydraulic material, and the dispersant of the present invention. The composition is a hydraulic material cement of ordinary cement, early-strength cement, blast furnace cement and the like as a main component, which contains blast furnace slag fine aggregate as essential, further,
It contains other fine aggregate, coarse aggregate and other additives (materials). As blast furnace slag fine aggregate, JIS A
5011 blast furnace slag fine aggregate.
Blast furnace slag fine aggregate, the concrete mix m ³ per 50
It is preferable to use 0 to 1500 kg.

Other additives (materials) used in the hydraulic composition include, for example, resin soap, saturated or unsaturated fatty acid, sodium hydroxystearate,
Lauryl sulfate, alkylbenzene sulfonic acid (salt), alkane sulfonate, polyoxyalkylene alkyl (phenyl) ether, polyoxyalkylene alkyl (phenyl) ether sulfate (salt), polyoxyalkylene alkyl (phenyl) ether phosphate (salt) , Protein material, alkenyl succinic acid,
AE agents such as α-olefin sulfonates; gluconic acid,
Oxycarboxylic acids such as glucoheptonic acid, arabonic acid, malic acid, citric acid, etc., sugars such as dextrins, monosaccharides, oligosaccharides, polysaccharides, etc., retarders such as sugar alcohols; foaming agents; thickeners; An AE water reducing agent; soluble calcium salts such as calcium chloride, calcium nitrite, calcium nitrate, calcium bromide and calcium iodide; chlorides such as iron chloride and magnesium chloride; sulfates; potassium hydroxide; sodium hydroxide; Fastener or accelerator such as carbonate, thiosulfate, formic acid (salt), alkanolamine; foaming agent; waterproofing agent such as resin acid (salt), fatty acid ester, oil and fat, silicone, paraffin, asphalt, wax; Agent;
Dimethylpolysiloxane-based, polyalkylene glycol fatty acid ester-based, mineral oil-based, oil-based, oxyalkylene-based, alcohol-based, amide-based antifoaming agents; antifoaming agents; melaminesulfonic acid formalin condensate-based, aminosulfonic acid-based, High-performance water reducing agents such as polycarboxylic acids and polymaleic acids; rust inhibitors such as nitrites, phosphates and zinc oxide; celluloses such as methylcellulose and hydroxyethylcellulose; natural such as β-1,3-glucan and xanthan gum -Soluble polymers, such as synthetic products, such as synthetic products, polyacrylamide, polyethylene glycol, ethylene oxide adduct of oleyl alcohol or a reaction product thereof with vinylcyclohexene diepoxide; polymer emulsions such as alkyl (meth) acrylate Blast furnace slag fine powder, fly ash, Admixtures such as fumes and the like.

The hydraulic composition of the present invention may be used in the fields of ready-mixed concrete, concrete vibration products, self-leveling, refractories, plaster, gypsum slurry, lightweight or heavy concrete, AE, repair, prepacked It is useful in any field of various concretes, such as for concrete, for trammy, for grout, and for cold.

[0024]

EXAMPLES The following evaluations were performed using the dispersants for blast furnace slag fine aggregate shown in Table 1. The molecular weights in Table 1 are weight-average molecular weights determined by gel permeation chromatography (standard substance: sodium polystyrene sulfonate conversion / water system). In Table 1, EO is ethylene oxide,
PO represents propylene oxide, and the number following () represents the average number of moles added.

[0025]

[Table 1]

(Evaluation method) In the concrete mix-1 and mix-2 shown in Table 2, the materials and the admixture were kneaded for 3 minutes by a forced mixer, and the fluidity and the like were adjusted by the following method. Was evaluated. The symbols and contents in Table 2 are shown below. W: Tap water C: Ordinary Portland cement Specific gravity = 3.16 S: Blast furnace slag fine aggregate Specific gravity = 2.66 G: Crushed stone (from Wakayama) Specific gravity = 2.63 s / a: Sand / (sand + gravel) Volume rate

[0027]

[Table 2]

The fluidity (slump value) is the amount of the dispersant added to the product of the present invention or the comparative product so as to be 19 ± 1 cm, and the foaming entrainer (mighty agent) so that the initial air amount is 4 ± 1%. AE-03: manufactured by Kao Corporation, and an antifoaming agent (antifoam E-20: manufactured by Kao Corporation) were added. In addition,
The slump value was measured according to JIS-A1101.

Measurement of the breathing rate is based on JIS-A11
According to the 23 method. As for the concrete state, the appearance of the concrete at the time of slump measurement was observed according to the following criteria. ++: Gravel is hardly conspicuous, and the shape of the slump cone is well maintained. +: Gravel is slightly conspicuous, but the shape of the slump cone is almost maintained.-: Sand is conspicuous, and the shape of the slump cone is collapsed. Table 3 shows the results for Formulation-1 and Table 4 shows the results for Formulation-2.

[0030]

[Table 3]

[0031]

[Table 4]

[0032]

As is clear from Tables 3 and 4, the concrete to which the dispersant of the present invention is added has less bleeding and excellent concrete uniformity even when blast furnace slag fine aggregate is used. Therefore, according to the present invention, it is possible to improve the workability of hydraulic material using blast furnace slag fine aggregate and obtain a homogeneous concrete structure.

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) C04B 103: 40 C04B 103: 40 F term (Reference) 4G012 PA04 PA29 PB16 PB36 PC01 4J027 AC03 AC04 AC06 AJ02 AJ06 BA02 BA03 BA04 BA05 BA06 BA13 BA14 BA30 CA11 CC02

Claims (4)

[Claims] 1. A dispersant for blast furnace slag fine aggregate containing a polymer containing a polyoxyalkylene group (average degree of condensation of oxyalkylene group: 2 to 300). 2. The polymer according to claim 1, wherein the polymer contains at least one vinyl monomer (a) containing an oxyalkylene group having 2 to 3 carbon atoms at an average degree of condensation of 2 to 300, and a carboxyl group, a sulfonic acid group or an amide. 2. The dispersant for blast furnace slag fine aggregate according to claim 1, which is a water-soluble copolymer obtained by polymerizing a monomer mixture containing at least one vinyl monomer (b) having a group. 3. The monomer (a) is a compound represented by the general formula (A), and the monomer (b) is a compound represented by the general formula (B) or (C)
The dispersant for blast furnace slag fine aggregate according to claim 2, which is a compound represented by the formula: Embedded image Wherein R ₁ and R ₂ are each a hydrogen atom or a methyl group,
m1 is a number of 0 to 2, AO is an oxyalkylene group having 2 to 3 carbon atoms, n is a number of 2 to 300, X is a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and n AOs are the same. But they may be different. [Chemical formula 2] Wherein R ₃ , R ₄ and R ₅ are each a hydrogen atom, a methyl group or — (CH ₂ ) _m2 COOM ₂ , R ₆ is a hydrogen atom or a methyl group, and M ₁ , M ₂ and Y are each a hydrogen atom Or, a cationic group, m2 represents a number of 0 to 2. ] 4. A hydraulic composition comprising a blast furnace slag fine aggregate, a hydraulic material, and the dispersant according to any one of claims 1 to 3.