KR101242729B1 - shrinkage-reducing cement dispersant and concret composition containing that - Google Patents

Abstract

The present invention is a compound having excellent cement dispersibility and shrinkage-resistance of polyoxyalkylene aryl ether (component A), maleic acid or fumaric acid ester (component B) of polyoxyalkylene alkyl ether, polyoxyethylene polyoxypropylene glycol Acrylic acid or methacrylic acid ester (C component), acrylic acid or methacrylic acid E: polyoxyalkylene alkyl ether of acrylic acid or methacrylic acid ester (component D) as molar ratio A: B: C: D is 1: 0.5 to 3: A shrinkage-type cement dispersant comprising a copolymer or an alkali salt thereof obtained by copolymerization at a ratio of 3: 1 to 1 to 1 to 3, and the concrete including the same has high dispersibility and increases the susceptibility to increase the strength when curing concrete. It is a compound composed of a single molecule, which has long-term storage stability, and provides shrinkage sensitivity to prevent cracking of hardened products, thereby increasing the strength and durability of concrete. .

Description

Shrink-reducing cement dispersant and concret composition containing that}

The present invention relates to a cement dispersant having shrinkage reducing properties and a concrete composition using the dispersant.

In order to obtain the conventional high strength concrete products, various dispersants have been proposed. For example, sodium lignin sulfonate, sodium polynaphthalene sulfonate, etc. have been used for a long time, and recently have polyoxyalkylene groups as shown in JP 2000-327385, 2003-165755, 2008-184344, etc. Polycarboxylic acid compounds have been proposed.

In addition, as shrinkage reducing agents for concrete products, various alkylene oxides mainly made of polyoxyalkylene aryl ethers and polyalkylene glycols disclosed in Japanese Patent Laid-Open No. 2008-31008, 2008-169085, 2009-180021, and the like. Additives have been proposed.

On the other hand, as a compound composed of a single molecule to exhibit the dispersibility and shrinkage-reduction of the cement, the addition of oligoalkylene glycol or polyvalent alkylene glycol to the side chains of polycarboxylic acid and salts thereof in Japanese Unexamined Patent Publication No. 2001-10853 and 1996-268741 Although disclosed, these are not enough dispersibility and shrinkage reduction.

 In addition, the shrinkage-type cement dispersant mixed with a known cement dispersant and a known shrinkage reducing agent is poor in long-term preservation stability.

The present inventors have studied to improve the shortcomings of the conventional shrinkage reduction cement dispersant is excellent cement as a compound composed of a single molecule The present invention was completed by preparing a novel compound having dispersibility and reducing shrinkage of concrete products.

The present invention provides a novel shrinkage reducing cement dispersant which has high dispersibility and high susceptibility to enable the production of high strength concrete products and at the same time give excellent shrinkage reduction to concrete products.

The present invention provides a cement dispersant and a concrete composition comprising the same that gives excellent cement dispersibility and shrinkage reduction of concrete.

The dry shrinkage reduction cement dispersant of the present invention is polyoxyalkylene aryl ether (component A) obtained by adding 1 mol of aryl alcohol and 1-50 mol of an alkylene oxide compound selected from ethylene oxide, propylene oxide and mixtures thereof,

One selected from maleic acid or fumaric acid to 1 mole of polyoxyalkylene alkyl ether obtained by adding 1 mole of alcohol having 1 to 5 carbon atoms and 1 to 50 moles of alkylene oxide compound selected from ethylene oxide, propylene oxide and mixtures thereof. Or a mixture of mono and diesters obtained by reacting two or more acids 0.5 to 1 mol (component B),

An acrylate compound obtained by reacting 1 to 2 mol of acrylic acid or methacrylic acid to 1 mol of polyoxyethylene polyoxypropylene glycol obtained by adding 1 to 50 mol of ethylene oxide to 1 mol of polypropylene glycol having an average molecular weight of 500 to 5000. (C component) and one or two or more monomers (component D) selected from acrylic acid, methacrylic acid and alkali salts thereof, wherein A: B: C: D is 1: 0.5 to 3: 0.01 It manufactures including the copolymer which is a compound obtained by copolymerization in the molar ratio of -1: 1-3, or its salt.

In addition, the shrinkage reducing cement dispersant of the present invention is acrylic acid or 1 mole of polyoxyalkylene alkyl ether obtained by adding 1 to 50 moles of ethylene oxide, propylene oxide, and mixtures thereof to 1 mole of C1-5 alcohol. It can be manufactured including the copolymer which is a compound obtained by carrying out a copolymerization reaction further including the compound (E component) obtained by making 1 mol of methacrylic acid react, or its salt. It is preferable that the said E component at this time carries out copolymerization reaction in the molar ratio of 1: 0.01-2 with respect to A component.

In addition, the shrinkage reduction cement dispersant of the present invention can be produced by neutralizing 50 to 80% by weight of the acid group of the copolymer obtained by copolymerizing the A component, B component, C component, D component and E component.

In this invention, ester of maleic acid or fumaric acid of the polyoxyalkylene alkyl ether which is B component is obtained as follows. First, polyoxyalkylene alkyl ether is ethylene oxide, propylene oxide and mixtures thereof in 1 mol of lower alcohols such as alcohols having 1 to 5 carbon atoms, for example, methyl alcohol, ethyl alcohol, isopropyl alcohol, butyl alcohol and pentyl alcohol. It is obtained by adding 1 to 50 moles under an alkali catalyst by a known method. At this time, it is preferable to add 10-30 mol of ethylene oxide to 1 mol of methyl alcohol. More preferably, from a mixture of 3 moles of ethylene oxide added to 1 mole of methyl alcohol, 1 mole of pure methyl alcohol obtained by distillation from ethoxylate to obtain a compound in which 3 moles of ethylene oxide is bound to 1 mole of pure methyl alcohol is obtained. 7-40 mol of ethylene oxide is further added to 3 mol of ethylene oxide-bonded compounds to obtain polyoxyethylene alkyl ether. This method is preferable because of its narrow molecular weight distribution. Although 1 mol of maleic anhydride is made to react with 1 mol of polyoxyethylene alkyl ethers obtained, ring-opening ester reaction is carried out, or 0.5 mol of maleic acid or fumaric acid is reacted with a known method, and diester reaction is carried out under an alkali catalyst, but B is obtained. It is more preferable to make 1 mol of maleic acid react.

In the present invention, acrylic acid or methacrylic acid ester of polyoxyethylene polyoxypropylene glycol which is a C component is polyoxyethylene obtained by adding 1-50 ethylene oxide to a polypropylene glycol having an average molecular weight of 500 to 5000 by a known method. It is obtained by making 1 mol of acrylic acid or methacrylic acid react with 1 mol of polyoxypropylene glycol by a well-known method. Preferably 1 to 2 mol of acrylic acid or methacrylic acid is added to 1 mol of polyoxyethylene polyoxypropylene glycol obtained by adding 2 to 20 mol of ethylene oxide to 1 mol of polypropylene glycol having an average molecular weight of 1000 to 3000 by a known method. It can be obtained by reacting. In addition, 1 to 10 moles of ethylene oxide may be added to acrylic acid or methacrylic acid, followed by addition to 20 to 60 moles of propylene oxide, followed by addition of 1 to 10 moles of ethylene oxide.

In this invention, acrylic acid or methacrylic acid ester of polyoxyalkylene alkyl ether which is E component can be obtained by making acrylic acid or methacrylic acid react with 1 mol of polyoxyalkylene alkyl ethers obtained by B as a well-known method. For example, 1 mole of methyl acrylate or methyl methacrylate is added to 1 mole of polyoxyethylene alkyl ether as an alkyl catalyst, and a solvent is added thereto, heated to reflux, followed by dehydration and de-methanol. After completion of the reaction, excess methyl acrylate or methacrylic acid is completed. It is obtained by distilling off methyl.

Preferably the present invention is polyoxyethylene aryl ether (component A) obtained by adding 1 mol of aryl alcohol and 5-30 mol of ethylene oxide

Fumaric acid mono and di [polyoxyethylenemethyl ether] esters (B) which are compounds obtained by reacting 0.5 to 1 mol of fumaric acid with 1 mol of polyoxyethylene methyl ether obtained by addition reaction of 1 mol of methanol and 10 to 50 mol of ethylene oxide (B ingredient)

An acrylate compound (component C), acrylic acid (component D1) and methanol 1 obtained by adding 4 to 10 mol of ethylene oxide to 1 mol of polypropylene glycol having an average molecular weight of 1000 to 3000, followed by adding 1 to 2.0 mol of methacrylic acid. In the copolymerization reaction of the acrylic acid ester (component E) of polyoxyethylene methyl ether which is a compound obtained by reacting 1 mol of acrylic acid with 1 mol of polyoxyethylene methyl ether obtained by adding 10 to 50 mol of ethylene oxide to the mole, The compound obtained by neutralizing 50-80 weight% of acidic groups in the copolymer obtained by copolymerizing B: C: D1: E in the molar ratio of 1: 0.5-3: 0.01-1: 1-3: 0.01-1 is contained. Can be prepared.

Moreover, this invention is polyoxyethylene aryl ether obtained by adding 5-30 mol of ethylene oxide to 1 mol of aryl alcohols (component A),

Fumaric acid mono and di [polyoxyethylenemethyl ether] esters (B) which are compounds obtained by reacting 0.5 to 1 mol of fumaric acid with 1 mol of polyoxyethylene methyl ether obtained by adding 10 to 20 mol of ethylene oxide to 1 mol of methanol. ingredient),

An acrylate compound (component C), acrylic acid (component D1) and methanol 1 obtained by adding 4 to 10 mol of ethylene oxide to 1 mol of polypropylene glycol having an average molecular weight of 1000 to 3000, followed by adding 1 to 1.2 mol of methacrylic acid. In the copolymerization reaction of methacrylic acid ester (E1 component) of polyoxyethylene methyl ether which is a compound obtained by reacting 1 mol of methacrylic acid with 1 mol of polyoxyethylene methyl ether obtained by adding 43 mol of ethylene oxide to moles, Including the compound obtained by neutralizing 60-80% of the acidic radicals of the compound obtained by copolymerizing said A: B: C: D1: E1 in the molar ratio of 1: 0.5-1: 0.01-1: 1.5-3: 0.5-2. Can be prepared.

The present invention is polyoxyalkylene aryl ether (component A) obtained by adding 1 to 50 moles of one selected from ethylene oxide, propylene oxide and a mixture thereof to 1 mole of aryl alcohol,

Maleic acid mono and di [polyoxyethylenemethyl ether] esters (component B), which are compounds obtained by reacting 0.5 to 1 mol of maleic acid with 1 mol of polyoxyethylene methyl ether obtained by adding 43 mol of ethylene oxide to 1 mol of methanol,

An acrylate compound obtained by reacting 1 to 2 mol of acrylic acid or methacrylic acid with 1 mol of polyoxyethylene polyoxypropylene glycol obtained by adding 1 to 50 mol of ethylene oxide to 1 mol of polypropylene glycol having an average molecular weight of 500 to 5000 ( Methacrylate of polyoxyethylene methyl ether, which is a compound obtained by reacting 1 mol of methacrylic acid with 1 mol of polyoxyethylene methyl ether obtained by adding 43 mol of ethylene oxide to 1 mol of acrylic acid (D1 component) and methanol. In copolymerizing acid ester (E1 component), the acid group of the compound obtained by copolymerizing said A: B: C: D1: E1 in the molar ratio of 1: 0.5-2: 0.01-1: 1.5-2: 0.5-2 It can be prepared including a compound obtained by neutralizing 60 to 80% by weight.

The copolymerization catalyst used in the copolymerization with A, B, C, D and E of the present invention is not particularly limited, but organic peroxides, inorganic peroxides, nitrile compounds, azo compounds, sulfonic acid compounds and the like can be used.

In addition, the chain transfer agent used in the present invention is not particularly limited, alkyl mercaptan, mercapto fatty acid, mercapto alcohol and the like can be used.

The acid value of the compound obtained by copolymerization with A, B, C, D and E of the present invention was measured and 50 to 100% by weight of the acid group of the acid value was caustic soda, caustic, magnesium hydroxide, ammonia, mono Ethanolamine, triethanolamine and the like may be neutralized with alkali using a single or a mixture of two or more kinds, but preferably 60 to 80% by weight of an acid group is neutralized with caustic soda. The acid value at this time can be measured by the method of KS M 0065 and the acid value of the present invention is KS M 0065 It was measured by the method and neutralized with alkali.

The present invention also provides a concrete composition containing a reduced shrinkage cement dispersant comprising a compound prepared according to the present invention.

The reduced shrinkage type cement dispersant prepared according to the present invention is not particularly limited, but may preferably be added to the cement in an amount of 0.2 to 10% by weight.

In addition, the reduced shrinkage type cement dispersant according to the present invention can be used simultaneously with other concrete additives unless the effect of the present invention is suppressed.

Other concrete additives include, but are not particularly limited to, known antifoaming agents, coagulation delay agents, coagulation accelerators and rust inhibitors.

Shrinkage reduction cement dispersant according to the present invention has the advantage of enabling the production of high-strength concrete products by increasing the efficiency of the work to be made of a compound composed of a single molecule to increase the work efficiency and the concrete, including the same .

In addition, the shrinkage reducing cement dispersant according to the present invention is a compound composed of a single molecule is not separated even after long-term storage is high long-term storage.

In addition, the shrinkage reduction cement dispersant according to the present invention has an advantage that can be made to give a high strength as well as reducing, preventing cracks by providing excellent shrinkage reduction to the concrete including the same.

In the following, examples are described for the purpose of detailed understanding of the invention, which is for illustrative purposes only and does not limit the scope of the invention.

The compound which obtained each component of this invention by the well-known method is shown as follows.

A-1: Polyoxyethylene aryl ether which is a compound obtained by adding 20 mol of ethylene oxides to 1 mol of aryl alcohols

A-2: Polyoxyethylene aryl ether which is a compound obtained by addition-reacting 10 mol of ethylene oxide to 1 mol of aryl alcohols.

A-3: Polyoxyethylene polyoxypropylene aryl ether which is a compound obtained by addition-reacting 10 mol of ethylene oxide and 2 mol of propylene oxide to 1 mol of aryl alcohols.

B-1: Maleic acid mono and di [polyoxyethylene methyl ether] ester which is a compound obtained by making 1 mol of maleic acid react with 1 mol of polyoxyethylene methyl ether obtained by adding 43 mol of ethylene oxides to 1 mol of methanol.

B-2: Fumaric acid mono and di [polyoxyethylene methyl ether] ester which are compounds obtained by making 0.75 mol of fumaric acid react with 1 mol of polyoxyethylene methyl ether obtained by adding 13 mol of ethylene oxides to 1 mol of methanol.

B-3: Mono- and di [polyoxyethylene maleic acid which are compounds obtained by reacting 0.8 mol of maleic acid with 1 mol of polyoxyethylene polyoxypropylene methyl ether obtained by addition reaction of 13 mol of ethylene oxide and 3 mol of propylene oxide to 1 mol of methanol. Polyoxypropylene methyl ether] ester

C-1: Compound mono and dipolyoxyethylene obtained by reacting 1 mol of methacrylic acid with 1 mol of polyoxyethylene polyoxypropylene glycol ether obtained by adding 5 mol of ethylene oxide to 1 mol of polypropylene glycol having an average molecular weight of 2000. Methacrylic acid ester of polyoxypropylene glycol (2000) ether

C-2: Polyoxyethylene polyoxypropylene glycol which is a compound obtained by making 1 mol of methacrylic acid react with 1 mol of polyoxyethylene polyoxypropylene glycol ethers obtained by adding 15 mol of ethylene oxide to polypropylene glycol of the average molecular weight 2000. Ether methacrylate ester

D-1 ： Acrylic acid

D-2 ： Methacrylic acid

D-3 ： Alkali salt of acrylic acid

D-4 ： Alkali salt of methacrylic acid

E-1: Methacrylic acid ester of polyoxyethylene methyl ether which is a compound obtained by making 1 mol of methacrylic acid react with 1 mol of polyoxyethylene methyl ether obtained by adding 43 mol of ethylene oxide to 1 mol of methanol.

E-2: Acrylic acid ester of polyoxyethylene methyl ether which is a compound obtained by making 1 mol of acrylic acid react with 1 mol of polyoxyethylene methyl ether obtained by adding 13 mol of ethylene oxide to 1 mol of methanol.

E-3: Polyoxyethylene polyoxy which is a compound obtained by making 1 mol of methacrylic acid react with 1 mol of polyoxyethylene polyoxypropylene methyl ethers obtained by adding 43 mol of ethylene oxide and 3 mol of propylene oxide to 1 mol of methanol. Methacrylic acid ester of propylene methyl ether

[Example 1]

Into a glass reactor equipped with a thermometer, a stirrer, a dropping device, a nitrogen introduction tube and a reflux cooling device, ammonium persulfate (0.25% of the total amount of the reactants) was added with ionized water and a copolymerization catalyst, and the inside of the reactor was replaced with nitrogen while stirring. It heated to 80 degreeC in nitrogen atmosphere. 3-mercaptopropionic acid (0.4% of the total amount of the reactants) was added dropwise with A-1, B-1, C-1, D-1, E-1 and a chain transfer agent, and the mixture was dropped for 1 hour at 80 ° C after completion of dropping. Stirring completed the polymerization reaction. The completed polymerization reaction product was neutralized with 45% sodium hydroxide aqueous solution to 6.5H6.5 to obtain a shrinkage reducing cement dispersant which was a polymer aqueous solution having a viscosity of 253 cps and a concentration of 50% by weight.

In Example 1, the molar ratio of A-1, B-1, C-1, D-1, and E-1 used for the reaction is 1.00: 1.25: 0.50: 2.00: 1.50.

By varying the components as described in Table 1 below in the same manner to prepare a shrinkage reducing cement dispersant which is a polymer aqueous solution in Examples 2-9 and Comparative Examples 1-3.

Reactant molar ratios of Examples 2-9 and Comparative Examples 1-3 Intermediate
Examples 2 to 9 Copolymers
[Comparison] Copolymer
2 3 4 5 6 7 8 9 One 2 3 A-1
A-2
A-3
1.00


1.00
1.00


1.00
1.00
1.00


1.00
1.00

0.10





B-1
B-2
B-3
1.25


1.25 0.75


0.63
0.88

0.75


0.63

0.88




0.10

C-1
C-2 0.50

0.50
0.15
0.08 0.23
0.15
0.08

0.23


D-1
D-2 2.00
2.00
2.00
1.50
2.50

2.00 1.50
2.50
3.00
4.00
3.50
E-1
E-2
E-3 1.50



1.50






2.00

0.63
0.88

1.00

1.00

1.00

Viscosity (cps) 316 216 114 113 118 240 218 278 491 513 47

[Evaluation of shrinkage reduction rate of polymer aqueous solutions prepared in Examples 1 to 9 and Comparative Examples 1 to 3]

For the shrinkage reduction test of the shrinkage reducing cement dispersant which is the polymer aqueous solution prepared in each of Examples 1 to 9 and Comparative Examples 1 to 3, concrete was prepared at the blending ratio as shown in Table 2 below. Put the same amount of cement dispersant (1.0wt% compared with cement) and use the FLOW CON-500 (polycarboxylic acid system, Woojin industry) as a high-performance reducing agent to adjust the amount of slump to meet the target slump (180 ± 10mm㎜). Was tested. Shrinkage was measured by the following equation by measuring the shrinkage length of the cured concrete of width × length × length (50mm × 50mm × 1000mm) for 8 weeks, and the reduction rate was measured. The results are summarized in Table 3.

Reduction rate (%) = [(Shrinkage after 8 weeks-Shrinkage after 8 weeks) / Shrinkage after no additive] × 100

Concrete mix ratio for shrinkage reduction test slump Air volume W / C
(%) S / a
(%) W C S G Shrinkage reducing agent
usage High Performance Supervisor
usage 180 ± 10mm 4.5 ± 0.5 47.2 47.0 151 320 847 967 C × 1.0% C × (0 ~ 1.2%)

(W: deionized water, C: cement (usually Portland cement, specific gravity 3.14), S: fine aggregate, G: coarse aggregate, a: aggregate (aggregate = sand + gravel), fine aggregate (river sand, specific gravity 2.55), coarse aggregate (Crushed gravel, specific gravity 2.58), SRA agent (addition of shrinkage reducing cement dispersant C × 1.0% of the present invention), Superplasticizer: FLOW CON-500 (polycarboxylic acid system, Woojin industry)

Reduction rate results of Examples 1 to 9 and Comparative Examples 1 to 3
Shrinkage reducing agent Shrinkage ( mm / 1000 mm )
High Performance Supervisor
usage 1 week 2 weeks 3 weeks 4 weeks 6 weeks 8 weeks Reduction rate Example 1 0.220 0.307 0.339 0.357 0.375 0.380 34.26%

same
Slump
Forming
rock
High performance
My
Usage

adjustment Example 2 0.216 0.310 0.337 0.358 0.381 0.386 33.14% Example 3 0.222 0.318 0.346 0.367 0.390 0.396 31.43% Example 4 0.230 0.330 0.359 0.381 0.405 0.411 28.86% Example 5 0.233 0.333 0.363 0.386 0.410 0.416 28.00% 6 0.238 0.341 0.372 0.395 0.420 0.426 26.29% Example 7 0.217 0.305 0.338 0.353 0.376 0.385 33.37% Example 8 0.212 0.297 0.328 0.346 0.365 0.369 36.12% Example 9 0.220 0.308 0.340 0.356 0.378 0.382 33.80% Comparative Example 1 0.351 0.453 0.497 0.519 0.541 0.550 4.76% Comparative Example 2 0.344 0.444 0.487 0.509 0.530 0.539 6.67% Comparative Example 3 0.336 0.442 0.485 0.508 0.528 0.536 7.19% No additives 0.369 0.476 0.522 0.545 0.568 0.578 0.00% C × 1.2%

As shown in the results of the reduction rate, the comparative example showed a small amount of shrinkage reduction rate in the comparative example, but the concrete including the shrinkage reducing agent of the embodiment of the present invention showed better shrinkage reduction rate than the comparative example. This excellent shrinkage reduction rate may have the advantage of reducing or preventing the breakdown of concrete.

[Evaluation of Susceptibility of Concrete Containing Shrinkage-Reducing Cement Dispersant That Is a Polymer Aqueous Solution Prepared in Examples 1 to 9 and Comparative Examples 1 to 3]

In order to evaluate the susceptibility of the concrete containing the shrinkage-reducing cement dispersant which is the polymer aqueous solution prepared in each of Examples 1 to 9 and Comparative Examples 1 to 3, the concrete was prepared at the compounding ratio as shown in Table 4 below, and the chemical chemistry for KS F 2560 Experiment was carried out by the admixture test method.

Put the same amount (1.0wt% of cement) SRA agent (shrinkage-reducing cement dispersant according to the present invention), in order to meet the desired slump (180 ± mmmm), change the W / C and the change in unit quantity accordingly Was calculated by the following equation to evaluate the susceptibility, and the results are summarized in Table 5.

Reduction ratio (%) = [(No additive unit quantity-Test unit quantity) / No additive unit quantity] × 100

Susceptibility test slump Air volume W / C
(%) S / a
(%) W C S G Shrinkage reducing agent
usage Plain 180 ± 10 mm 1.5 ± 0.5 62.8 48.0 201 320 841 922 No additives Susceptibility test formulation 1801 ± 0 mm 4.5 ± 0.5 variable 47.0 variable 320 variable variable C × 1.0%

(W: water, C: cement (usually Portland cement, specific gravity 3.14), S: fine aggregate, G: coarse aggregate, a: aggregate (aggregate = sand + gravel), fine aggregate (river's yarn, specific gravity 2.55), coarse aggregate ( Crusher

Brown, specific gravity 2.58), SRA agent (addition of shrinkage reducing cement dispersant C × 1.0% of the present invention), Superplasticizer: FLOW CON-500 (polycarboxylic acid system, Woojin industry)

Reduction rate evaluation results of Examples 1 to 9 and Comparative Examples 1 to 3 Shrinkage reducing agent
(C × 1.0%) Susceptibility Test W / C (%) Unit quantity (kg) Reduction rate (%) Example 1 50.0 160 20.6 Example 2 49.7 159 20.9 Example 3 49.1 157 21.9 Example 4 47.5 152 24.4 Example 5 48.1 154 23.4 6 47.8 153 23.9 Example 7 49.4 158 21.4 Example 8 50.3 161 19.9 Example 9 49.4 158 21.4 Comparative Example 1 48.4 155 22.9 Comparative Example 2 49.1 157 21.9 Comparative Example 3 47.8 153 23.9 No additives 62.1 201 0

As shown in Table 5, the concrete to which the shrinkage reducing cement dispersant of the present invention showed excellent results similar to those of the conventional high performance water reducing agent. This shows that the shrinkage-resistance and the function as a high-performance water-reducing agent are not impaired, indicating that the shrinkage-type cement dispersant of the present invention has no shrinkage-resistance and no sensitivity at all.

In addition, the shrinkage reduction cement dispersant prepared in Example was stored for 6 months at room temperature, it was confirmed that the product is uniform and not separated. It is believed that the shrinkage reducing cement dispersant according to the invention is a single compound.

Claims (8)

Polyoxyalkylene aryl ether (component A) obtained by adding 1 mol of an aryl alcohol and 1-50 mol of an alkylene oxide compound selected from ethylene oxide, propylene oxide and mixtures thereof;
One selected from maleic acid or fumaric acid to 1 mole of polyoxyalkylene alkyl ether obtained by adding 1 mole of alcohol having 1 to 5 carbon atoms and 1 to 50 moles of alkylene oxide compound selected from ethylene oxide, propylene oxide and mixtures thereof. Or a mixture of mono and diesters obtained by reacting two or more acids 0.5 to 1 mol (component B),
An acrylate compound obtained by reacting 1 to 2 mol of acrylic acid or methacrylic acid to 1 mol of polyoxyethylene polyoxypropylene glycol obtained by adding 1 to 50 mol of ethylene oxide to 1 mol of polypropylene glycol having an average molecular weight of 500 to 5000. (C component) and one or two or more monomers (component D) selected from acrylic acid, methacrylic acid and alkali salts thereof, wherein A: B: C: D is 1: 0.5 to 3: 0.01 A shrinkage reducing cement dispersant comprising a copolymer or a salt thereof which is a compound obtained by copolymerization at a molar ratio of ˜1: 1 to 3. The method of claim 1,
1 mole of acrylic acid or methacrylic acid to 1 mole of polyoxyalkylene alkyl ether obtained by adding an alkylene oxide compound selected from 1 to 50 moles of ethylene oxide, propylene oxide and a mixture thereof to 1 mole of C1-5 alcohol A shrinkage reducing cement dispersant comprising a copolymer or a salt thereof, which is a compound obtained by performing a copolymerization reaction further comprising a compound (E component) obtained by reacting. The method of claim 2,
The said E component is a shrinkage reduction cement dispersing agent containing the copolymer or its salt which is a compound obtained by copolymerizing with a molar ratio of 1: 0.01-2 with respect to A component. The method of claim 3, wherein
The salt of the copolymer is a shrinkage reducing cement dispersant prepared by neutralizing 50 to 80% by weight of the acid group. The method of claim 2,
Polyoxyethylene aryl ether (component A) obtained by adding 1 mol of aryl alcohol and 5-30 mol of ethylene oxide,
Fumaric acid mono and di [polyoxyethylenemethyl ether] esters (B) which are compounds obtained by reacting 0.5 to 1 mol of fumaric acid with 1 mol of polyoxyethylene methyl ether obtained by addition reaction of 1 mol of methanol and 10 to 50 mol of ethylene oxide (B ingredient),
An acrylate compound (component C), acrylic acid (component D1) and methanol 1 obtained by adding 4 to 10 mol of ethylene oxide to 1 mol of polypropylene glycol having an average molecular weight of 1000 to 3000, followed by adding 1 to 1.2 mol of methacrylic acid. In the copolymerization reaction of the acrylic acid ester (component E) of polyoxyethylene methyl ether which is a compound obtained by reacting 1 mol of acrylic acid with 1 mol of polyoxyalkylene methyl ether obtained by adding 10 to 50 mol of ethylene oxide to the mole. A compound prepared by neutralizing 50 to 80% by weight of an acid group in a copolymer obtained by copolymerizing A: B: C: D1: E in a molar ratio of 1: 0.5 to 3: 0.01 to 1: 1 to 0.01 to 1 Shrinkage reduction cement dispersant containing. The method of claim 2,
Polyoxyethylene aryl ether obtained by adding 5-30 mol of ethylene oxide to 1 mol of aryl alcohols (A component),
Fumaric acid mono and di [polyoxyethylenemethyl ether] esters (B) which are compounds obtained by reacting 0.5 to 1 mol of fumaric acid with 1 mol of polyoxyethylene methyl ether obtained by adding 10 to 20 mol of ethylene oxide to 1 mol of methanol. ingredient),
An acrylate compound (component C), acrylic acid (component D1) and methanol 1 obtained by adding 4 to 10 mol of ethylene oxide to 1 mol of polypropylene glycol having an average molecular weight of 1000 to 3000, followed by adding 1 to 1.2 mol of methacrylic acid. In the copolymerization reaction of methacrylic acid ester of polyoxyethylene methyl ether (component E1), which is a compound obtained by reacting 1 mole of methacrylic acid with 1 mole of polyoxyalkylene alkyl ether obtained by adding 43 moles of ethylene oxide to mole. The compound obtained by neutralizing 60-80 weight% of the acidic radicals of the compound obtained by copolymerizing said A: B: C: D1: E1 in the molar ratio of 1: 0.5-1: 0.01-1: 1.5-3: 0.5-2 Shrinkage reduction cement dispersant containing. The method of claim 2,
Polyoxyalkylene aryl ether (component A) obtained by adding 1 to 50 moles of one selected from ethylene oxide, propylene oxide and a mixture thereof to 1 mole of aryl alcohol,
Maleic acid mono and di [polyoxyethylene methyl ether] esters (component B1), which are compounds obtained by reacting 0.5 mol to 1 mol of maleic acid with 1 mol of polyoxyethylene methyl ether obtained by adding 43 mol of ethylene oxide to 1 mol of methanol,
An acrylate compound obtained by reacting 1 to 2 mol of acrylic acid or methacrylic acid to 1 mol of polyoxyethylene polyoxypropylene glycol obtained by adding 1 to 50 mol of ethylene oxide to 1 mol of polypropylene glycol having an average molecular weight of 500 to 5000. Meta of polyoxyethylene methyl ether which is a compound obtained by making 1 mol of methacrylic acid react with 1 mol of polyoxyethylene methyl ether obtained by adding (C component), acrylic acid (D1 component), and 43 mol of ethylene oxide to 1 mol of methanol. The acid group of the compound obtained by copolymerizing the said acrylic acid ester (E1 component) by copolymerizing said A: B1: C: D1: E1 in the molar ratio of 1: 0.5-2: 0.01-1: 1.5-2: 0.5-2 A shrinkage reducing cement dispersant containing a compound obtained by neutralizing 60 to 80% by weight of a resin. A concrete composition comprising a reduced shrinkage cement dispersant comprising a compound prepared according to any one of claims 1 to 7.