CN113165976A - Additive for hydraulic composition and hydraulic composition - Google Patents
Additive for hydraulic composition and hydraulic composition Download PDFInfo
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- CN113165976A CN113165976A CN201880099777.4A CN201880099777A CN113165976A CN 113165976 A CN113165976 A CN 113165976A CN 201880099777 A CN201880099777 A CN 201880099777A CN 113165976 A CN113165976 A CN 113165976A
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B24/00—Use of organic materials as active ingredients for mortars, concrete or artificial stone, e.g. plasticisers
- C04B24/24—Macromolecular compounds
- C04B24/26—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B28/00—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements
- C04B28/02—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements containing hydraulic cements other than calcium sulfates
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
- Y02W30/50—Reuse, recycling or recovery technologies
- Y02W30/91—Use of waste materials as fillers for mortars or concrete
Abstract
An additive for hydraulic compositions which can reduce the influence of fine particles and argillaceous substances contained in aggregate and has high material segregation resistance. An additive for hydraulic compositions and a hydraulic composition, comprising: has a structural unit composed of acrylic acid and/or its salt and has a mass-average molecular weight MAA component A of 1000 or more and less than 100000; and a structural unit derived from acrylic acid and/or a salt thereof and having a mass-average molecular weight MBIs a component B of 100000 to 50000000.
Description
Technical Field
The present invention relates to an additive for hydraulic compositions. More specifically, the present invention relates to an additive for hydraulic compositions which can reduce the influence of fine particles or argillaceous substances contained in aggregate, has high material segregation resistance, and can be suitably used for cement compositions and the like.
Background
In order to impart fluidity to hydraulic compositions such as mortar and concrete, lignin sulfonic acid-based dispersants, naphthalene sulfonic acid-based dispersants, melamine sulfonic acid-based dispersants, polycarboxylic acid-based dispersants, and the like have been used as dispersants in the production of the hydraulic compositions. In recent years, hydraulic compositions having further improved fluidity have been used in many cases for the purpose of improving filling properties, saving labor and improving workability. As such a hydraulic composition, for example, a concrete having high fluidity, such as a high-fluidity concrete having a slump flow of about 500nm to 700nm, or a medium-fluidity concrete having a slump flow of about 350nm to 500nm, can be used.
Various techniques have been proposed to obtain such hydraulic compositions. For example, patent document 1 proposes that fluidity and material segregation resistance be imparted to concrete by using an admixture obtained by blending a specific polycarboxylic acid-based dispersant and a copolymer of a carboxylic acid monomer and a (meth) acrylate. Further, patent document 1 discloses: the specific polycarboxylic acid-based dispersant and the copolymer of a carboxylic acid monomer and a (meth) acrylate ester as raw material components may be combined and supplied as a one-pack type admixture.
In addition, patent document 2 proposes a concrete having high filling properties and high fluidity by using a specific low-substitution hydroxypropylcellulose.
Documents of the prior art
Patent document
Patent document 1: japanese patent laid-open publication No. 2001-89212
Patent document 2: japanese laid-open patent publication No. 4-139047
Disclosure of Invention
Problems to be solved by the invention
As the aggregate to be blended in the hydraulic composition, coarse aggregate, fine aggregate, and the like can be used. As such coarse aggregates and fine aggregates, natural aggregates such as gravel and sand produced from rivers, mountains, oceans, lands, and the like, which are formed of rocks by natural action, may be used; or crushed stone and crushed sand obtained by manually crushing rocks using a crusher or the like.
From the viewpoint of resource conservation in the process of continuous depletion of high-quality natural aggregates or in consideration of the influence on the environment during washing, the natural aggregates may be used as they are without washing off fine particles or clayey substances adhering to the natural aggregates within a quality-allowable range.
In addition, fine particles, clayey crushed stone, and crushed sand, which are generated when rock is artificially crushed to produce crushed stone and crushed sand, may be adhered to the crushed stone and crushed sand.
If these fine particles and clayey particles are attached to the aggregate, the amount of the dispersant to be added needs to be increased. If the amount of the dispersant added is increased, bleeding out occurs more disadvantageously. In addition, when a hydraulic composition having a predetermined slump flow and high fluidity is to be obtained, there is a problem that the materials are easily separated.
Aggregates vary in composition and quality depending on the place or time of collection. The fluidity of the hydraulic composition is not constant due to the difference in the composition or the quality of the aggregate, and there is a problem that the amount of the admixture to be added needs to be changed in order to obtain a predetermined fluidity.
Further, when hydroxypropyl cellulose having a low substitution degree is used, there is a problem that the compatibility with the water reducing agent component is low and a single aqueous solution cannot be obtained.
The techniques disclosed in patent documents 1 and 2 cannot solve the above-described problems. Accordingly, an object of the present invention is to provide an additive for hydraulic compositions which can reduce the influence of fine particles and argillaceous substances contained in aggregate and has high material segregation resistance, even when the fine particles, argillaceous substances, and the like adhered to the aggregate remain unwashed.
Means for solving the problems
The present inventors have conducted studies to solve the above problems and found that an additive for hydraulic compositions, which contains a specific polymer, is suitable and accurate. According to the present invention, the following additive for hydraulic compositions is provided.
[1] An additive for hydraulic compositions comprising the following component A and the following component B,
component A: has a structural unit composed of acrylic acid and/or its salt and has a mass-average molecular weight MAA polymer of 1000 or more and less than 100000,
component B: having a structural unit derived from acrylic acid and/or a salt thereof and having a mass-average molecular weight MBIs a polymer of 100000-50000000 inclusive.
[2] The additive for hydraulic compositions according to the above [1], wherein the mass ratio A: B of the component A to the component B is 1:99 to 99: 1.
[3] The additive for hydraulic compositions according to the above [1], further comprising a carboxylic acid copolymer as the component C.
[4] The additive for hydraulic compositions according to the above [3], wherein the total mass% of the component A and the component B is 0.1 to 25% based on the mass of the component C.
[5] A hydraulic composition comprising the additive for hydraulic compositions according to any one of [1] to [4 ].
[6] The hydraulic composition according to the above [5], which further comprises a binder.
[7] The hydraulic composition according to [6], wherein the total mass part of the component A and the component B is 0.00005 to 0.04 parts by mass based on 100 parts by mass of the binder.
ADVANTAGEOUS EFFECTS OF INVENTION
According to the additive for hydraulic compositions of the present invention, even when the fine particles, clay and the like adhered to the aggregate are not washed away, the effect of the fine particles and clay contained in the aggregate can be reduced and the material separation resistance can be improved.
Detailed Description
Hereinafter, embodiments of the present invention will be described. However, the present invention is not limited to the following embodiments. Therefore, it is to be understood that the following embodiments may be appropriately modified or improved based on the common general knowledge of those skilled in the art without departing from the scope of the present invention. In the following examples and the like, "%" means "% by mass" and "parts" means "parts by mass" unless otherwise specified.
The additive for hydraulic compositions of the present embodiment is an additive for hydraulic compositions containing the component a and the component B.
The component a and the component B used in the additive for hydraulic compositions of the present embodiment are polymers having a structural unit formed of acrylic acid and/or a salt thereof. The type of the acrylic acid salt is not particularly limited, and examples thereof include alkali metal salts such as sodium salt and potassium salt, alkaline earth metal salts such as calcium salt and magnesium salt, and amine salts such as ammonium salt, diethanolamine salt and triethanolamine salt. From the viewpoint of easy handling and availability, sodium salts and ammonium salts are preferred, and sodium salts are more preferred. The acrylic acid and/or its salt may be used alone or in combination of 2 or more.
The mass-average molecular weight M of the polymer of component A used in the additive for hydraulic compositions of the present embodimentAIs 1000 or more and less than 100000, preferably 1000 or more and 50000 or less, more preferably 1000 or more and 30000 or less, and further preferably 1000 or more and 10000 or less.
The mass-average molecular weight M of the polymer of component B used in the additive for hydraulic compositions of the present embodimentBIs 100000 or more and 50000000 or less, preferably 300000 or more and 30000000 or less, more preferably 500000 or more and 20000000 or less, and further preferably 800000 or more and 10000000 or less.
In the additive for hydraulic compositions of the present embodiment, the concentrations of the component a and the component B are not particularly limited, but if the ratio of the component a is too high, a sufficient separation-inhibiting effect cannot be obtained, and if the ratio of the component B is too high, a change in the fluidity of the hydraulic composition due to fine particles in the aggregate increases, and from the viewpoint of preventing the above phenomenon, the mass ratio a: B of the component a to the component B is preferably 1:99 to 99:1, more preferably 50:50 to 99:1, further preferably 75:25 to 99:1, further preferably 80:20 to 99:1, and particularly preferably 80:20 to 96: 4.
The additive for hydraulic compositions of the present embodiment preferably further contains a carboxylic acid copolymer as component C.
The carboxylic acid copolymer used as component C of the additive for hydraulic compositions of the present embodiment includes those having the following structural units: a structural unit composed of an unsaturated carboxylic acid monomer and/or a salt thereof, and a structural unit composed of an unsaturated monomer having in the molecule thereof a polyoxyalkylenel group composed of 1 to 300 oxyalkylene units having 2 to 4 carbon atoms.
Examples of the unsaturated carboxylic acid monomer and/or a salt thereof include (meth) acrylic acid, crotonic acid, maleic acid (anhydride), itaconic acid (anhydride), fumaric acid and/or a salt thereof. The unsaturated dicarboxylic acid monomer having 2 or more carboxyl groups in one molecule may have an ester bond, an amide bond, or the like in addition to one carboxylic acid or a salt thereof. The kind of the unsaturated carboxylic acid salt is not particularly limited, and examples thereof include alkali metal salts such as sodium salt and potassium salt, alkaline earth metal salts such as calcium salt and magnesium salt, and amine salts such as ammonium salt, diethanolamine salt and triethanolamine salt.
Examples of the unsaturated monomer having a polyoxyalkylene group comprising 1 to 300 oxyalkylene units having 2 to 4 carbon atoms in the molecule include α -vinyl- ω -hydroxy (poly) oxybutylene (poly) oxyethylene, α -allyl- ω -methoxy- (poly) oxyethylene (poly) oxypropylene, α -allyl- ω -hydroxy- (poly) oxyethylene, α -allyl- ω -hydroxy- (poly) oxypropylene, α -allyl- ω -hydroxy- (poly) oxyethylene, α -methallyl- ω -methoxy- (poly) oxyethylene, α -methallyl- ω -hydroxy- (poly) oxyethylene, poly (poly) oxypropylene, poly (poly) oxyethylene), poly (meth) oxypropylene), poly (meth) propylene, or (meth) propylene, poly (meth) propylene, or the like, Alpha-methallyl-omega-acetyl- (poly) oxyethylene, alpha- (3-methyl-3-butenyl) -omega-hydroxy- (poly) oxyethylene, alpha- (3-methyl-3-butenyl) -omega-butoxy- (poly) oxyethylene, alpha- (3-methyl-3-butenyl) -omega-hydroxy- (poly) oxyethylene (poly) oxypropylene, alpha- (3-methyl-3-butenyl) -omega-acetyl- (poly) oxypropylene, alpha-acryloyl-omega-hydroxy- (poly) oxyethylene, alpha-acryloyl-omega-methoxy- (poly) oxyethylene, alpha-acryloyl-omega-hydroxy- (poly) oxyethylene, alpha-methacryloyl-omega-methoxy- (poly) oxyethylene, Alpha-acryloyl-omega-butoxy- (poly) oxyethylene, alpha-acryloyl-omega-methoxy- (poly) oxyethylene (poly) oxypropylene, alpha-methacryloyl-omega-hydroxy- (poly) oxyethylene, alpha-methacryloyl-omega-methoxy- (poly) oxyethylene, alpha-methacryloyl-omega-butoxy- (poly) oxyethylene, alpha-acryloyl-omega-methoxy- (poly) oxyethylene (poly) oxypropylene, alpha-methacryloyl-omega-hydroxy- (poly) oxyethylene (poly) oxypropylene, alpha-methacryloyl-omega-acetyl- (poly) oxyethylene (poly) oxypropylene, reactive imino groups in polyalkylene polyamines, reactive amino groups in polyalkylene polyamines, and mixtures thereof, Polyalkylene polyamine monomers having an unsaturated bond such as a (meth) acryloyl group in the molecule thereof and alkylene oxide (alkylene oxide) added to an active amino group, and polyamidopolyamine monomers having an unsaturated bond such as a (meth) acryloyl group in the molecule thereof and having an active imino group, amino group, or amide residue of polyamidopolyamine obtained by condensing dibasic acid and polyalkylene polyamine.
The mass average molecular weight of the carboxylic acid copolymer as the component C is preferably 2000 to 500000, more preferably 5000 to 200000.
In the additive for hydraulic compositions of the present embodiment, the total mass% of the component a and the component B is preferably 0.1% to 25%, more preferably 0.2% to 15%, even more preferably 0.3% to 10%, and even more preferably 0.5% to 5% with respect to the mass of the component C.
Next, the hydraulic composition of the present embodiment will be described. The hydraulic composition of the present embodiment includes the additive for hydraulic compositions of the present embodiment.
The method of adding the additive for hydraulic compositions to the hydraulic composition may be carried out by adding the component A, the component B and the component C independently or simultaneously. The components a, B and C may be added to the hydraulic composition slurry as powders, or the components a, B and C may be added to the hydraulic composition slurry in a state of being dispersed or dissolved in a liquid shrinkage reducing agent, a liquid defoaming agent or the like, or the components a, B and C may be added to the hydraulic composition slurry in a state of being dissolved in water. The manner of addition of each component may be different. For example, the component a and the component B may be added as powders, and the component C may be added in a state of being dispersed in a liquid shrinkage reducing agent, a liquid defoaming agent, or the like, or may be added in another manner.
The carboxylic acid-based copolymer as the component C may be used as an aqueous solution, and when used as an aqueous solution, the pH of a1 mass% aqueous solution of the component C is preferably 2 to 7, more preferably 2 to 6, and even more preferably 2 to 5, from the viewpoint of compatibility with the components a and B.
The hydraulic composition of the present embodiment is prepared by using the additive for hydraulic compositions of the present embodiment described above, and is preferably a cement composition such as cement paste, mortar, concrete, or the like. The cement composition uses at least cement as a binder, and may use cement alone or cement in combination with a pozzolanic substance or a fine powder mixed material having latent hydraulic properties. Examples of such cements include various portland cements such as ordinary portland cement, medium-heat portland cement, low-heat portland cement, early-strength portland cement, super-early-strength portland cement, and sulfate-resistant portland cement, and various blended cements such as blast furnace cement and fly ash cement. Examples of the fine powder mixture include blast furnace slag fine powder, silica fume, fly ash, limestone fine powder, and the like. Further, an expanding material, gypsum, or the like may be contained.
The hydraulic composition of the present embodiment preferably also contains aggregate. As the aggregate, any suitable aggregate such as a fine aggregate and a coarse aggregate can be used. Among these aggregates, river sand, mountain sand, land sand, quartz sand, crushed sand, blast furnace slag fine aggregate and the like are exemplified as the fine aggregate, and river gravel, mountain gravel, land gravel, crushed stone, blast furnace slag coarse aggregate and the like are exemplified as the coarse aggregate.
In the hydraulic composition of the present embodiment, the total mass part of the component a and the component B is preferably 0.00005 to 0.04 mass part, more preferably 0.0002 to 0.03 mass part, further preferably 0.0002 to 0.02 mass part, further preferably 0.0003 to 0.01 mass part, and particularly preferably 0.0004 to 0.008 mass part, based on 100 mass parts of the binder.
The hydraulic composition of the present embodiment may suitably contain, for example, an AE regulator composed of an anionic surfactant, an oxyalkylene (oxyalkylene) based defoaming agent, a retarder composed of a hydroxycarboxylic acid salt, a hardening accelerator composed of an alkanolamine, a drying shrinkage reducing agent composed of a polyoxyalkylene alkyl ether, an antiseptic composed of an isothiazoline compound, a water repellent composed of a higher fatty acid derivative, a rust preventive composed of a nitrite, and the like, within a range in which the effects thereof are not impaired.
Examples
Hereinafter, examples and the like are given to further illustrate the configuration and effects of the present invention, but the present invention is not limited to the examples. In the following examples, "%" means "% by mass" and "parts" means "parts by mass" unless otherwise specified.
Test class 1 (acrylic acid and/or salt polymer thereof as component A and component B)
The polymers of acrylic acid and/or its salts used are summarized and shown in table 1.
[ Table 1]
In the context of table 1, the following,
a-1: sodium polyacrylate (Toya synthetic Co., Ltd アロン T-210)
A-2: polyacrylic acid (polyacrylic acid 5,000 manufactured by Heguang pure chemical industries Co., Ltd.)
A-3: polyacrylic acid (polyacrylic acid 25,000 manufactured by Heguang pure chemical industries Co., Ltd.)
B-1: polyacrylic acid (polyacrylic acid 250,000 manufactured by Heguang pure chemical industries Co., Ltd.)
B-2: polyacrylic acid (polyacrylic acid 1,000,000, manufactured by Wako pure chemical industries, Ltd.)
B-3: sodium polyacrylate (Toya synthetic Co., Ltd. アロン A-20P-X)
R-1: hydroxypropyl methylcellulose (メトローズ Hi90SH30000, manufactured by shin Etsu chemical industries Co., Ltd.)
R-2: hydroxypropyl methylcellulose (メトローズ Hi90SH100000 manufactured by shin-Etsu chemical Co., Ltd.)
d-1: structural unit formed from sodium acrylate
d-2: structural units formed from acrylic acid
d-3: structural units formed from acrylic acid
d-4: structural units formed from acrylic acid
d-5: structural units formed from acrylic acid
d-6: structural unit formed from sodium acrylate
Test class 2 (production of carboxylic acid copolymer as component C)
Production example 1{ production of Carboxylic acid-based copolymer (PC-1) }
In a reaction vessel equipped with a thermometer, a stirrer, a dropping funnel and a nitrogen gas introduction tube (hereinafter, the same reaction vessel is used), 250g of distilled water and 330g of α - (3-methyl-3-butenyl) - ω -hydroxy-poly (n ═ 50) oxyethylene were put and uniformly dissolved while stirring, and then the atmosphere was replaced with nitrogen gas, and the temperature of the reaction system was maintained at 65 ℃ by a hot water bath. Next, 16g of 1% hydrogen peroxide water was dropped over 3 hours, and at the same time, an aqueous solution obtained by uniformly dissolving 30g of acrylic acid in 80g of ion-exchanged water was dropped over 3 hours, and at the same time, an aqueous solution obtained by dissolving 2g of L-ascorbic acid and 3g of thioglycolic acid in 14g of ion-exchanged water was dropped over 4 hours. Subsequently, the temperature of the reaction system was maintained at 65 ℃ for 2 hours, and the polymerization reaction was terminated. Then, a 30% aqueous sodium hydroxide solution was added to the reaction system to adjust the pH to 3, and the concentration was adjusted to 40% with ion-exchanged water, thereby obtaining a reaction mixture. The reaction mixture was analyzed by Gel Permeation Chromatography (GPC), and as a result, the mass average molecular weight was 35000. The reaction product was used as a carboxylic acid copolymer (PC-1).
Production example 2{ production of carboxylic acid-based copolymer (PC-2) }
150g of distilled water was placed in a reaction vessel, the atmosphere was replaced with nitrogen, and the temperature of the reaction system was maintained at 60 ℃ under a nitrogen atmosphere. Next, 150g of distilled water, 20g of methacrylic acid, 320g of α -hydroxy- ω -methacryloyl-poly (n ═ 2) propylene poly (n ═ 113) oxyethylene, 10g of hydroxyethyl acrylate, and 3.5g of 3-mercaptopropionic acid were uniformly mixed to prepare an aqueous monomer mixture solution. It took 4 hours to simultaneously drop the aqueous monomer mixture solution and 24g of a 10% aqueous sodium persulfate solution into the reaction vessel to perform radical copolymerization, and it took further 1 hour to drop 6g of a 10% aqueous sodium persulfate solution to perform reaction. Subsequently, the temperature of the reaction system was maintained at 60 ℃ for 1 hour, thereby carrying out a radical copolymerization reaction. Next, the reaction system was cooled to room temperature, and then an aqueous sodium hydroxide solution was added thereto to adjust the pH to 5, and the concentration was adjusted to 40% with distilled water, thereby obtaining a reaction mixture. The reaction mixture was analyzed by Gel Permeation Chromatography (GPC), and as a result, the mass average molecular weight was 43000. The reaction mixture was used as a carboxylic acid copolymer (PC-2).
Production example 3{ production of Carboxylic acid-based copolymer (PC-3) }
150g of distilled water was placed in a reaction vessel, the atmosphere was replaced with nitrogen, and the temperature of the reaction system was maintained at 60 ℃ under a nitrogen atmosphere. Next, 150g of distilled water, 35g of methacrylic acid, 300g of α -methoxy- ω -methacryloyl-poly (n ═ 23) oxyethylene, 5g of methyl acrylate, and 3.5g of 3-mercaptopropionic acid were uniformly mixed to prepare an aqueous monomer mixture solution. It took 4 hours to simultaneously drop the aqueous monomer mixture solution and 24g of a 10% aqueous sodium persulfate solution into the reaction vessel to perform radical copolymerization, and it took further 1 hour to drop 6g of a 10% aqueous sodium persulfate solution to perform reaction. Subsequently, the temperature of the reaction system was maintained at 60 ℃ for 1 hour, thereby carrying out a radical copolymerization reaction. Next, the reaction system was cooled to room temperature, and then an aqueous sodium hydroxide solution was added thereto to adjust the pH to 4, and the concentration was adjusted to 40% with distilled water, thereby obtaining a reaction mixture. The reaction mixture was analyzed by Gel Permeation Chromatography (GPC), and as a result, the mass average molecular weight was 43000. The reaction mixture was used as a carboxylic acid copolymer (PC-3).
Test type 3 (measurement of Mass average molecular weights of component A and component B)
The mass average molecular weights of component a and component B were measured by the following methods. The results are shown in table 1.
[ measurement of the Mass average molecular weights of component A and component B ]
The mass average molecular weight of the polymer of acrylic acid and/or a salt thereof was measured by gel permeation chromatography-multi-angle light scattering method (GPC-MALS method) and/or gel permeation chromatography (GPC method), and the conditions were set as follows. The polymers of acrylic acid and/or its salts used are shown in table 1.
When the mass average molecular weight of polyacrylic acid exceeds 500,000, the measurement by GPC cannot be performed, and therefore, GPC-MALS method is used for a mass average molecular weight of polyacrylic acid exceeding 500,000. In B-1, the molecular weight difference between the GPC-MALS method and the GPC method is within. + -. 3%, and the results are considered to be the same.
[ measurement conditions ]
[ GPC-MALS method ]
A detector: differential Refractometer (RI), multi-angle light scatter detector (MALS)
Column: ohpak SB-807HQ + SB-806M HQ manufactured by Showa electrician
Eluent: 0.1M Tris buffer (pH 0.9, 0.1M potassium chloride added)/acetonitrile mixed solvent (mixing volume ratio: 7/3)
Flow rate: 0.5 mL/min
Column temperature: 40 deg.C
[ GPC method ]
A detector: differential Refractometer (RI)
Column: ohpak SB-G + SB-806M HQ manufactured by Showa electrician
Eluent: 50mM aqueous sodium nitrate solution
Flow rate: 0.7 mL/min
Column temperature: 40 deg.C
Standard substance: sodium polyacrylate manufactured by アジレント Co
[ measurement of the Mass-average molecular weight of component C ]
The mass average molecular weight of the carboxylic acid copolymer as component C was measured by Gel Permeation Chromatography (GPC), and the conditions were set as follows.
[ measurement conditions ]
A detector: differential Refractometer (RI)
Column: ohpak SB-G + SB-806M HQ manufactured by Showa electrician
Eluent: 50mM aqueous sodium nitrate solution
Flow rate: 0.7 mL/min
Column temperature: 40 deg.C
Standard substance: アジレント polyethylene glycol/oxide (PEG/PEO)
Test type 4 (confirmation of compatibility)
When the carboxylic acid copolymer of component C was 20%, the mixture was sufficiently stirred and mixed at the ratio of component a to component B shown in table 2, and the compatibility of the solution was judged by visual observation using the following criteria. Tap water was used to adjust the concentration of the solution.
(compatibility judging Standard)
A: the extent of precipitation or sedimentation cannot be recognized
B: thin turbidity was confirmed
C: confirmed that precipitation or sedimentation was observed
[ Table 2]
In the context of table 2, the following,
in addition, the method is as follows: the ratio of B-2: mass ratio of B-3B-2: b-3 was used in a ratio of 50: 50.
In addition, 2: r-1 and R-2 are added after replacing with the component B.
Test class 5 (preparation of concrete composition as Hydraulic composition)
Concrete compositions were prepared as follows under the blending conditions described in tables 2 and 3. Ordinary portland cement (density 3.16 g/cm) as a binder was charged into a 50L disk-type forced kneading mixer3) Fly ash (density 2.29 g/cm)32.3% of intense heat loss and fine powder of blast furnace slag (density 2.88 g/cm)3) Then, Dajing Sichuan water system produced land sand (density 2.58 g/cm) as fine aggregate was poured in3) And crushed stone produced by Okazaki as coarse aggregate (density 2.68 g/cm)3) Bentonite (manufactured by Wako pure chemical industries, Ltd.) was further charged into blend No.2 of Table 3 and kneaded for 10 seconds. Subsequently, an antifoaming agent (trade name AFK-2 manufactured by bamboo fat and oil company) was added in a range of 0.005 to 0.01 parts by mass to 100 parts by mass of the binder so that the target slump flow was 600 ± 30mm and the air amount was 2% or less, and the additive for hydraulic compositions used in test category 4 was added together with kneading water and kneaded for 90 seconds. It should be noted that the additives and the defoaming agent are considered as part of the water.
[ Table 3]
The kneading and testing of the blended materials were carried out in an environment in which the material temperature was set to 20. + -. 3 ℃, the room temperature was set to 20. + -. 3 ℃ and the humidity was set to 60% or more. With respect to the prepared concrete compositions of the respective examples, slump flow immediately after kneading, air amount immediately after kneading, separation resistance immediately after kneading, and bleeding were determined as follows. The results of blend No.1 are shown in Table 4, and the results of blend No.2 are shown in Table 5.
Slump flow: the concrete composition immediately after kneading was measured in accordance with JIS-A1150 after lifting a slump cone for 3 minutes.
Air amount: the concrete composition immediately after kneading was measured in accordance with JIS-A1128.
Separation resistance: for the concrete composition immediately after kneading, after lifting the slump cone for 3 minutes, by visual observation and the following criteria were applied.
(criterion for separation resistance)
A: very good (aggregate and mortar, slurry without separation)
B: good (aggregate and mortar, slurry slightly separated)
C: poor (aggregate and mortar-slurry separation)
D: very poor (significant separation of aggregate from mortar)
Bleed-out: measured according to JIS-A1123.
(determination Standard for bleeding)
A: very good (leaching rate of 0.00 to 4.00%)
B: good (leaching rate of 4.01 to 6.00%)
C: poor (leaching rate over 6.00%)
[ Table 4]
In the context of table 4, the results are,
in addition, the method is as follows: the total mass part (solid content) of the component (A) and the component (B) per 100 mass parts of the binder
In addition, 2: only part by mass (solid content) of the component (C) per 100 parts by mass of the binder
[ Table 5]
In the context of table 5, the results are,
in addition, the method is as follows: the total mass part (solid content) of the component (A) and the component (B) per 100 mass parts of the binder
In addition, 2: only part by mass (solid content) of the component (C) per 100 parts by mass of the binder
(results)
As shown in table 2, examples 1 to 10 including component a and component B showed superior compatibility compared to comparative examples 7 and 8 including hydroxypropyl methylcellulose instead of component B without component (a). In addition, as shown in table 4, examples 11 to 20 including component a and component B showed sufficient separation resistance and the amount of oozing was small, as compared with comparative examples 11 to 15 not including component a but having only component B and comparative example 16 not including component B but having only component a. Further, as shown in table 5, examples 21 to 30 containing component a and component B showed sufficient separation resistance and the amount of oozing was small, as compared with comparative examples 21 to 25 containing no component a and only component B, and comparative example 26 containing no component B and only component a. Further, comparative examples 17, 18, 27 and 28, which did not contain component A and contained hydroxypropyl methylcellulose instead of component B, were poor in compatibility.
Industrial applicability
The additive for hydraulic compositions of the present invention can be used as an additive in the production of hydraulic compositions.
Claims (7)
1. An additive for hydraulic compositions comprising the following component A and the following component B,
component A: has a structural unit composed of acrylic acid and/or its salt and has a mass-average molecular weight MAA polymer of 1000 or more and less than 100000,
component B: having a structural unit derived from acrylic acid and/or a salt thereof and having a mass-average molecular weight MBIs a polymer of 100000-50000000 inclusive.
2. The additive for hydraulic compositions according to claim 1, wherein the mass ratio A: B of the component A to the component B is from 1:99 to 99: 1.
3. The additive for hydraulic compositions according to claim 1 or 2, further comprising a carboxylic acid copolymer as the component C.
4. The additive for hydraulic compositions according to claim 3, wherein the total mass% of component A and component B is 0.1 to 25% based on the mass of component C.
5. A hydraulic composition comprising the additive for hydraulic compositions according to any one of claims 1 to 4.
6. The hydraulic composition according to claim 5, further comprising a binding material.
7. The hydraulic composition according to claim 6, wherein the total mass part of the component A and the component B is 0.00005 to 0.04 parts by mass with respect to 100 parts by mass of the binder.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| PCT/JP2018/044380 WO2020115790A1 (en) | 2018-12-03 | 2018-12-03 | Additive for hydraulic composition, and hydraulic composition |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN113165976A true CN113165976A (en) | 2021-07-23 |
| CN113165976B CN113165976B (en) | 2023-09-12 |
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ID=70974164
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201880099777.4A Active CN113165976B (en) | 2018-12-03 | 2018-12-03 | Additive for hydraulic composition and hydraulic composition |
Country Status (4)
| Country | Link |
|---|---|
| JP (1) | JP7148170B2 (en) |
| CN (1) | CN113165976B (en) |
| TW (1) | TW202021926A (en) |
| WO (1) | WO2020115790A1 (en) |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1154953A (en) * | 1995-07-13 | 1997-07-23 | 株式会社日本触媒 | Cement dispersing agent, prepn, method and composition using said cement dispersing agent |
| JP2001089212A (en) * | 1999-09-13 | 2001-04-03 | Nippon Shokubai Co Ltd | Liquid cement admixture and production thereof |
| EP1344754A2 (en) * | 2002-03-11 | 2003-09-17 | Kao Corporation | Admixture for a hydraulic composition |
| WO2005007773A1 (en) * | 2003-07-18 | 2005-01-27 | Toagosei Co., Ltd. | Additive for drilling fluid and drilling fluids containing the same |
| CN102239193A (en) * | 2008-12-08 | 2011-11-09 | 可泰克斯有限合伙公司 | Use, as an agent for improving the handleability of an aqueous formulation based on hydraulic binders, of a (meth)acrylic comb copolymer and of an associative acrylic thickener |
| WO2017221737A1 (en) * | 2016-06-21 | 2017-12-28 | 竹本油脂株式会社 | Concrete composition and cured concrete object |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP6649811B2 (en) | 2016-03-09 | 2020-02-19 | 株式会社日本触媒 | Additive for hydraulic composition and concrete composition |
-
2018
- 2018-12-03 CN CN201880099777.4A patent/CN113165976B/en active Active
- 2018-12-03 WO PCT/JP2018/044380 patent/WO2020115790A1/en active Application Filing
- 2018-12-03 JP JP2020558693A patent/JP7148170B2/en active Active
-
2019
- 2019-01-02 TW TW108100095A patent/TW202021926A/en unknown
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1154953A (en) * | 1995-07-13 | 1997-07-23 | 株式会社日本触媒 | Cement dispersing agent, prepn, method and composition using said cement dispersing agent |
| JP2001089212A (en) * | 1999-09-13 | 2001-04-03 | Nippon Shokubai Co Ltd | Liquid cement admixture and production thereof |
| EP1344754A2 (en) * | 2002-03-11 | 2003-09-17 | Kao Corporation | Admixture for a hydraulic composition |
| WO2005007773A1 (en) * | 2003-07-18 | 2005-01-27 | Toagosei Co., Ltd. | Additive for drilling fluid and drilling fluids containing the same |
| CN102239193A (en) * | 2008-12-08 | 2011-11-09 | 可泰克斯有限合伙公司 | Use, as an agent for improving the handleability of an aqueous formulation based on hydraulic binders, of a (meth)acrylic comb copolymer and of an associative acrylic thickener |
| WO2017221737A1 (en) * | 2016-06-21 | 2017-12-28 | 竹本油脂株式会社 | Concrete composition and cured concrete object |
Also Published As
| Publication number | Publication date |
|---|---|
| WO2020115790A1 (en) | 2020-06-11 |
| JPWO2020115790A1 (en) | 2021-09-27 |
| CN113165976B (en) | 2023-09-12 |
| TW202021926A (en) | 2020-06-16 |
| JP7148170B2 (en) | 2022-10-05 |
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