CN112969672B - Additive for hydraulic composition and hydraulic composition - Google Patents
Additive for hydraulic composition and hydraulic composition Download PDFInfo
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- CN112969672B CN112969672B CN201880099354.2A CN201880099354A CN112969672B CN 112969672 B CN112969672 B CN 112969672B CN 201880099354 A CN201880099354 A CN 201880099354A CN 112969672 B CN112969672 B CN 112969672B
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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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- Curing Cements, Concrete, And Artificial Stone (AREA)
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Abstract
Provided are an additive for hydraulic compositions and a hydraulic composition, which can reduce bleeding while maintaining dispersibility, slump retention and separation resistance of the hydraulic composition. The additive for hydraulic compositions contains a copolymer (A) which has a structure derived from a vinyl monomer comprising a structural unit (1) and a structural unit (2), has a structure derived from a hydrophobic chain transfer agent containing a sulfur atom, and has a mass average molecular weight as measured by gel permeation chromatography and calculated as polyethylene glycol of 100000 to 2000000 inclusive.
Description
Technical Field
The present invention relates to an additive for hydraulic compositions and a hydraulic composition. More specifically, the present invention relates to an additive for hydraulic compositions and a hydraulic composition, which can reduce bleeding while maintaining dispersibility, slump retention property, and separation resistance of hydraulic compositions such as cement, mortar, and concrete.
Background
Conventionally, various additives have been proposed for improving the physical properties of hydraulic compositions, for example, improving the dispersibility of hydraulic compositions such as cement, mortar and concrete, improving slump retention, and suppressing the generation of bleeding water (reducing bleeding) (patent document 1).
Documents of the prior art
Patent document
Patent document 1: japanese patent laid-open No. 2001-89212
Disclosure of Invention
Problems to be solved by the invention
However, the conventional additive for hydraulic compositions has the following problems: the bleeding cannot be reduced while maintaining the dispersibility, slump-retaining property and separation resistance of the hydraulic composition.
The present invention addresses the problem of providing an additive for hydraulic compositions and a hydraulic composition, which can reduce bleeding while maintaining the dispersibility, slump retention properties, and separation resistance of hydraulic compositions.
Means for solving the problems
The present inventors have conducted studies to solve the above problems and found that an additive for hydraulic compositions containing a specific component is suitable. The present invention provides the following additive for hydraulic compositions and hydraulic compositions.
[1] An additive for hydraulic compositions, comprising the following copolymer (A),
copolymer (a): a copolymer having a structure derived from a vinyl monomer comprising a structural unit (1) and a structural unit (2), having a structure derived from a hydrophobic chain transfer agent containing a sulfur atom, and having a mass average molecular weight, as measured by gel permeation chromatography, of 100000 to 2000000 inclusive in terms of polyethylene glycol,
structural unit (1): a structural unit formed by one or more monomers selected from the group represented by the following general formula 1,
structural unit (2): a structural unit formed from an unsaturated carboxylic acid and/or a salt thereof, wherein 80 to 100 mol% of the unsaturated carboxylic acid and/or a salt thereof is formed from one or two or more selected from (meth) acrylic acid and/or a salt thereof,
[ chemical formula 1]
(wherein, in the formula, R 1 、R 2 And R 3 Identical or different, represent a hydrogen atom or a methyl group; r is 4 The same or different, represent hydrogen or a hydrocarbon group having 1 to 30 carbon atoms; p represents an integer of 0 or 1; q represents an integer of 0 to 2; AO represents an oxy group having 2 to 18 carbon atomsAn alkylene group; n is an average addition mole number of AO, and represents a value of 1 to 300. ).
[2] The additive for hydraulic compositions according to [1], which has the following structure: the structure derived from the hydrophobic chain transfer agent has an alkyl chain, and at least one end of the structure derived from the hydrophobic chain transfer agent is bonded to a main chain end of the structure derived from the vinyl monomer via a sulfur atom.
[3] The additive for hydraulic compositions according to [1] or [2], wherein the mass average molecular weight of the copolymer (A) is 100000 to 600000.
[4] The additive for hydraulic compositions according to [2] or [3], wherein the number of carbon atoms of the alkyl chain is from 8 to 22.
[5] The additive for hydraulic compositions according to any one of [1] to [4], wherein the mass ratio of the structural unit (2) to the structural unit (1) is structural unit (2)/structural unit (1) =30/70 to 1/99.
[6] The additive for hydraulic compositions according to any one of [1] to [5], further comprising the copolymer (B),
copolymer (B): a copolymer having a structure derived from a vinyl monomer containing the structural unit (1) and the structural unit (2), and having a mass average molecular weight in terms of polyethylene glycol as measured by gel permeation chromatography of 5000 or more and less than 100000.
[7] The additive for hydraulic compositions according to [6], wherein the mass average molecular weight Ma of the copolymer (A) and the mass average molecular weight Mb of the copolymer (B) satisfy the following relational expression:
Ma-Mb≧80000。
[8] the additive for hydraulic compositions according to [6] or [7], wherein the mass ratio of the copolymer (A) to the copolymer (B) is copolymer (A)/copolymer (B) =1/99 to 30/70.
[9] A hydraulic composition comprising the additive for hydraulic compositions as defined in any one of [1] to [8 ].
ADVANTAGEOUS EFFECTS OF INVENTION
The additive for hydraulic compositions of the present invention has the effect of reducing bleeding while maintaining dispersibility, slump retention, and separation resistance.
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 according to the embodiment of the present invention contains the following copolymer (A).
The copolymer (a) used in the present embodiment has a structure derived from a vinyl monomer containing the structural unit (1) and the structural unit (2).
First, the structural unit (1) will be explained. The structural unit (1) is a structural unit formed from one or more monomers selected from the group represented by the following general formula 1.
[ chemical formula 2]
In the general formula 1, R 1 、R 2 And R 3 The same or different, represents a hydrogen atom or a methyl group. R 4 The same or different, represents hydrogen or a hydrocarbon group having 1 to 30 carbon atoms. Examples of the hydrocarbon group having 1 to 30 carbon atoms include an alkyl group having 1 to 30 carbon atoms, an alkenyl group having 2 to 30 carbon atoms, an aryl group having 6 to 30 carbon atoms and a benzene ring, and the like. From the viewpoint of further exhibiting the effect of the present invention, a hydrogen atom or a hydrocarbon group having 1 to 8 carbon atoms is preferable, and a hydrogen atom or a hydrocarbon group having 1 to 4 carbon atoms is more preferable.
In formula 1, p is an integer of 0 or 1. q is an integer of 0 to 2.
In the general formula 1, AO is an oxyalkylene group having 2 to 18 carbon atoms, preferably an oxyalkylene group having 2 to 4 carbon atoms, more preferably an oxyalkylene group having 2 to 3 carbon atoms. Examples of AO include oxyethylene, oxypropylene, oxybutylene and oxystyrene. Among these, oxyethylene, oxypropylene and oxybutylene are preferable, and oxyethylene and oxypropylene are more preferable. When AO is 2 or more species, it may be any of a random adduct, a block adduct and an alternate adduct. In order to maintain the water solubility of the copolymer, in formula 1, it is preferable that 50 mol% or more of the total oxyalkylene groups are oxyethylene groups; more preferably, 90 mol% or more of the total oxyalkylene groups are oxyethylene groups. In the general formula 1, n represents an average addition mole number of AO, and is a number of 1 to 300, preferably a number of 1 to 200, more preferably a number of 1 to 150.
Preferred examples of the monomer represented by the general formula 1 include polyethylene glycol mono (meth) acrylate, (poly) propylene (poly) ethylene glycol mono (meth) acrylate, methoxypolyethylene glycol (meth) acrylate, methoxy (poly) ethylene (poly) propylene glycol mono (meth) acrylate, butoxy (poly) ethylene glycol mono (meth) acrylate, (poly) ethylene glycol (poly) butylene glycol vinyl ether, polyethylene glycol monoallyl ether, (poly) ethylene glycol mono (2-methyl-2-propenyl) ether, polyethylene glycol mono (3-methylbutenyl) ether, and polyethylene (poly) propylene glycol mono (2-methyl-2-propenyl) ether. The monomer represented by the general formula 1 that forms the structural unit (1) may be used in 1 kind or 2 or more kinds.
Next, the structural unit (2) will be explained. The structural unit (2) is a structural unit formed from an unsaturated carboxylic acid and/or a salt thereof. Examples of the unsaturated carboxylic acid and/or a salt thereof that forms the structural unit (2) include (meth) acrylic acid, maleic acid (anhydride), fumaric acid, itaconic acid (anhydride), citraconic acid, crotonic acid, mono (2- (meth) acryloyloxyethyl) succinate, mono (2- (meth) acryloyloxypropyl) succinate, and a salt thereof. The 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, triethanolamine salt and triisopropanolamine salt. The unsaturated carboxylic acid and/or salt thereof forming the structural unit (2) may be used in 1 kind or 2 or more kinds.
As the unsaturated carboxylic acid and/or a salt thereof forming the structural unit (2), 80 to 100 mol% of the total of all the unsaturated carboxylic acids and/or salts thereof is one or more selected from (meth) acrylic acid and/or salts thereof; preferably, 90 to 100 mol% of the total of all the unsaturated carboxylic acids and/or salts thereof is one or more selected from (meth) acrylic acid and/or salts thereof; more preferably, 95 to 100 mol% of the total of all the unsaturated carboxylic acids and/or salts thereof is one or more selected from (meth) acrylic acid and/or salts thereof.
In order to sufficiently obtain the effect of reducing bleeding, the mass ratio of the structural unit (2) to the structural unit (1) in the vinyl monomer is preferably structural unit (2)/structural unit (1) =30/70 to 1/99, more preferably 20/80 to 5/95.
The copolymer (a) used in the present embodiment has a structure derived from a hydrophobic chain transfer agent containing a sulfur atom. Here, the structure having a hydrophobic chain transfer agent derived from a sulfur atom refers to a structure having a hydrophobic chain transfer agent derived from a sulfur atom at the terminal of the copolymer, and refers to a structure including a hydrophobic chain transfer agent derived from a hydrophobic chain transfer agent introduced into the main chain by a chain transfer reaction after removing a hydrogen radical from the main chain of the copolymer. More specifically, the following structure: the structure derived from the hydrophobic chain transfer agent containing a sulfur atom has a hydrophobic group, and at least one end is bonded to the end of the main chain derived from the structure of the vinyl monomer via the sulfur atom. Such a copolymer (a) is also produced by polymerizing one or two or more monomers selected from the monomers represented by the general formula 1 and an unsaturated carboxylic acid and/or a salt thereof in water in the presence of a hydrophobic chain transfer agent containing a sulfur atom.
The structure derived from the hydrophobic chain transfer agent containing a sulfur atom is a structure formed by the hydrophobic chain transfer agent containing a sulfur atom. Specific examples thereof include alkyl mercaptans such as n-dodecyl mercaptan, octadecyl mercaptan, hexadecyl mercaptan, 2-ethylhexyl mercaptan, tert-dodecyl mercaptan and docosyl mercaptan, alkyl mercaptocarboxylates such as octyl thioglycolate and octyl 3-mercaptopropionate, and the like. In order to sufficiently obtain the effect of reducing the overflow, an alkylthiol is preferable, and an alkylthiol having an alkyl chain of 8 to 22 carbon atoms is more preferable. Among them, n-dodecylmercaptan, octadecylmercaptan, hexadecylmercaptan, 2-ethylhexyl mercaptan, t-dodecylmercaptan, and docosylthiol mercaptan are preferable.
The content of the copolymer having a structure derived from the hydrophobic chain transfer agent containing a sulfur atom is preferably 10% by mass or more, and more preferably 40% by mass or more, relative to 100% by mass of the copolymer (a).
The copolymer (A) has a mass-average molecular weight, as measured by gel permeation chromatography, of 100000 to 2000000 in terms of polyethylene glycol. If the mass average molecular weight is less than 100000, dispersibility in the hydraulic composition may be exhibited, and the dispersion retentivity may be lowered; if the mass average molecular weight exceeds 2000000, the dispersion of the hydraulic composition may be greatly inhibited. From the viewpoint of dispersibility, dispersion retentivity, and the effect of reducing overflow, the lower limit of the mass average molecular weight is preferably 100000 or more, more preferably 150000 or more, further preferably 200000 or more, and the upper limit is preferably 2000000 or less, more preferably 1000000 or less, further preferably 600000 or less, and particularly preferably 500000 or less.
The copolymer (a) may contain a structural unit formed from other monomers. Other monomers may be used in 1 or 2 or more. Such a monomer is not particularly limited as long as it can be copolymerized with at least one of the monomers forming the structural unit (1) and the structural unit (2), and examples of such a monomer include (meth) acrylates such as methyl (meth) acrylate and butyl (meth) acrylate, (meth) acrylamides such as N, N-dimethyl (meth) acrylamide, (meth) acrylonitriles such as unsaturated cyanides, unsaturated dicarboxylic esters obtained by a monoester or diester of an unsaturated dicarboxylic acid such as maleic acid or fumaric acid and an alkyl or alkenyl alcohol having 1 to 22 carbon atoms, amide monomers obtained by a monoamide or diamide of an unsaturated carboxylic acid or unsaturated dicarboxylic acid and an amine having 1 to 22 carbon atoms, polyamide polyamine monomers obtained by condensing an alkyl dicarboxylic acid and polyethylene polyamine, polyamide polyamine monomers obtained by adding ethylene oxide or propylene oxide to a nitrogen atom having an active hydrogen, salts of a sulfonic acid monomer such as (meth) allyl sulfonic acid or vinyl sulfonic acid and salts thereof, and salts of a bis- (2-acryloyloxy) phosphoric acid monomer such as ethyl (2-methacryloyloxy) phosphate, and salts of a bis- (2-acryloyloxy) phosphoric acid monomer.
It is preferable that the copolymer (a) contains a structural unit formed from other monomers in a proportion of 0 to 10 mass% in the entire structural unit.
Next, a method for producing the copolymer (a) will be described. Examples of the method for producing the copolymer (a) include: a method of polymerizing the vinyl monomer in the presence of a radical polymerization initiator having a radical generating site, and the like. In a method of polymerizing a vinyl monomer in the presence of a radical polymerization initiator having a radical generation site, a radical is generated from a radical generation site such as an azo group by heat or the like, and polymerization is started. Examples of the radical polymerization initiator used for radical polymerization include peroxides such as hydrogen peroxide, ammonium persulfate, sodium persulfate, and potassium persulfate, and azo compounds such as 2,2-azobis (2-amidinopropane) dihydrochloride and 2,2-azobis (isobutyronitrile), and the kind thereof is not particularly limited as long as it is decomposed at a polymerization temperature to generate radicals. These may be used in combination with a reducing substance such as sulfite or L-ascorbic acid, or an amine as a redox initiator. The amount of the radical polymerization initiator to be used may be appropriately adjusted depending on the kind thereof.
The radical polymerization reaction is preferably carried out in aqueous solution polymerization using water as a solvent because a hydraulic composition such as cement is used as an aqueous solution. The aqueous solution polymerization may be a batch type or a continuous type, or a combination of 2 or more of these. From the viewpoint of economy, the concentration of the aqueous solution at the time of radical polymerization reaction is preferably 10 to 80% by mass, more preferably 20 to 80% by mass, and still more preferably 30 to 80% by mass. The concentration of the aqueous solution is represented by mass% represented by the following formula (1).
[ mathematical formula 1]
The reaction temperature in the radical polymerization reaction is not particularly limited as long as it is appropriately set according to the kind of the radical polymerization initiator, but is preferably 0 ℃ to 120 ℃, more preferably 20 ℃ to 100 ℃, and still more preferably 50 ℃ to 90 ℃.
It is important to use a hydrophobic chain transfer agent containing a sulfur atom as the additive for hydraulic compositions according to the embodiment of the present invention. In the case where a sulfur atom-containing hydrophobic chain transfer agent is not used, a copolymer having a structure derived from a vinyl monomer comprising the structural unit (1) and the structural unit (2) and a structure derived from a sulfur atom-containing hydrophobic chain transfer agent does not undergo polymerization, and bleeding may not be reduced while maintaining dispersibility, slump retention property, and separation resistance of the obtained hydraulic composition. As such a hydrophobic chain transfer agent containing a sulfur atom, the above-mentioned examples can be used.
In addition, it is preferable to use other hydrophobic chain transfer agent or hydrophilic chain transfer agent in addition to the hydrophobic chain transfer agent containing a sulfur atom. Although not particularly limited, examples of the hydrophilic chain transfer agent include water-soluble thiols such as mercaptoethanol, thioglycerol, thioglycolic acid, mercaptopropionic acid, 2-mercaptopropionic acid, 3-mercaptopropionic acid, thiomalic acid, and 2-mercaptoethanesulfonic acid, primary alcohols such as 2-aminopropane-1-ol, secondary alcohols such as isopropyl alcohol, lower oxides and salts thereof such as phosphorous acid, hypophosphorous acid, and salts thereof (e.g., sodium hypophosphite and potassium hypophosphite), or sulfurous acid, hydrogen sulfite, disulfidenesulfonic acid, and metabisulfite, and salts thereof (e.g., sodium sulfite, potassium sulfite, sodium bisulfite, potassium disulfite, and potassium metabisulfite). As other hydrophobic chain transfer agents, it is preferable to use a halide such as carbon tetrachloride, carbon tetrabromide, methylene chloride, bromoform, bromotrichloroethane; unsaturated hydrocarbon compounds such as α -methylstyrene dimer, α -terpinene, γ -terpinene, dipentene, and terpinolene, and particularly, hydrophilic chain transfer agents are preferably used in combination from the viewpoint of reducing bleeding, and among these, water-soluble thiols are preferable, and 3-mercaptopropionic acid, thioglycolic acid, and thioglycerol are particularly preferable.
In order to effectively obtain the desired effect, the amount of the sulfur atom-containing hydrophobic chain transfer agent to be used is preferably 1 to 100 mol%, more preferably 10 to 100 mol%, and still more preferably 40 to 80 mol%, relative to the total amount of the chain transfer agents to which the sulfur atom-containing hydrophobic chain transfer agent, the other hydrophobic chain transfer agents, and the hydrophilic chain transfer agent are added.
The method for adding each monomer component used for radical polymerization to the reaction vessel is not particularly limited, and may be, for example, any of the following methods: a method of charging the total amount into the reaction vessel at once at an initial stage; a method of charging the total amount into the reaction vessel in divided or continuous manner; a method in which a part of the reaction mixture is charged into a reaction vessel at the initial stage of the reaction and the remaining part is charged into the reaction vessel in portions or continuously. The radical polymerization initiator, the sulfur atom-containing hydrophobic chain transfer agent, the other hydrophobic chain transfer agent, and the hydrophilic chain transfer agent may be charged into the reaction vessel from the beginning, may be added dropwise to the reaction vessel, or may be combined.
The additive for hydraulic compositions according to the embodiment of the present invention preferably further contains the following copolymer (B) in addition to the copolymer (a).
The copolymer (B) used in the present embodiment preferably has a structure derived from a vinyl monomer containing the structural unit (1) and the structural unit (2).
The mass average molecular weight of the copolymer (B) in terms of polyethylene glycol as measured by gel permeation chromatography is 5000 or more and less than 100000, and more preferably 6000 or more and less than 70000, from the viewpoint of dispersibility of the hydraulic composition.
The copolymer (B) preferably further contains a structural unit formed from the above-mentioned other monomer. The proportion of each structural unit in the copolymer (B) may be appropriately set, and is not particularly limited, but is preferably the same as the proportion of the copolymer (a).
Next, a method for producing the copolymer (B) will be described. The copolymer (B) can be produced by the same method as the method for producing the copolymer (a). In the production of the copolymer (B), the hydrophilic chain transfer agent is preferably used.
In the additive for hydraulic compositions according to the embodiment of the present invention, the mass average molecular weight Ma of the copolymer (a) and the mass average molecular weight Mb of the copolymer (B) preferably satisfy the relational expression Ma-Mb ≧ 80000, more preferably satisfy the relational expression Ma-Mb ≧ 100000, still more preferably satisfy the relational expression Ma-Mb ≧ 150000, and still more preferably satisfy the relational expression Ma-Mb ≧ 200000.
In addition, the mass ratio of the above-mentioned copolymer (a) to the above-mentioned copolymer (B) is preferably copolymer (a)/copolymer (B) =1/99 to 30/70, more preferably 2/98 to 25/85.
Next, a hydraulic composition according to an embodiment of the present invention will be described. The hydraulic composition of the present embodiment is a hydraulic composition such as cement paste, mortar, concrete, or the like prepared by using the additive for hydraulic compositions of the present embodiment described above. The hydraulic composition of the present embodiment uses at least cement as a binder, and may use cement alone, or may use 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, early strength portland cement, medium thermal portland cement, and low thermal portland cement, and various mixed cements such as blast furnace cement, fly ash cement, and silica cement. Examples of the fine powder mixture include blast furnace slag fine powder, silica fume, fly ash, and the like.
In the hydraulic composition of the present embodiment, various fine aggregates and coarse aggregates can be used. Further, an AE adjusting agent, an antifoaming agent, a retarder, a hardening accelerator, a drying shrinkage reducing agent, a preservative, a water repellent, a rust preventive, and the like may be used in combination according to the purpose.
In the hydraulic composition of the present embodiment, the water/binder ratio is preferably 20% or more and less than 100% (mass ratio), more preferably more than 35% and less than 70% (mass ratio).
In the hydraulic composition of the present embodiment, the amount of the copolymer (a) to be used in the additive for hydraulic compositions of the present embodiment is preferably 0.0001 to 1 part by mass, more preferably 0.001 to 0.5 part by mass in terms of solid content, relative to 100 parts by mass of the binder composed of cement or 100 parts by mass of the binder composed of a mixture of cement and fine powder.
In the production of the hydraulic composition of the present embodiment, the additive for hydraulic compositions of the present embodiment may be used alone as it is or may be used in the form of an aqueous solution. The additive for hydraulic compositions may be added together with the kneading water at the time of preparing the hydraulic composition, or may be added at once or in several times at the time of kneading the hydraulic composition.
Examples
Hereinafter, examples and the like are described to more specifically explain the configuration and effects of the present invention, but the present invention is not limited to these examples.
Test class 1 (Synthesis of copolymer (A))
Synthesis of copolymer (PCA-1)
In a 1000mL round bottom flask equipped with a stirring blade, a stirrer, a nitrogen introduction tube, and a dropping funnel, 274.5g of ion-exchanged water, 179.5g of α -methacryloyl- ω -methoxy-poly (n = 45) oxyethylene, 19.9g of methacrylic acid, 0.20g of 3-mercaptopropionic acid, and 0.38g of n-dodecylmercaptan were placed, and uniformly dissolved while stirring, and then the atmosphere was replaced with nitrogen gas, and the temperature of the reaction system was adjusted to 70 ℃ by passing through a hot water bath. Then, a solution prepared by diluting 1.2g of 35% hydrogen peroxide water with 18.0g of ion-exchanged water was added to the reaction system to start the polymerization reaction. The temperature of the reaction system was maintained at 70 ℃ for 2 hours to conduct polymerization. Then, a solution prepared by diluting 0.4g of 35% hydrogen peroxide water with 6.0g of ion-exchanged water was added to the reaction system, and the temperature of the reaction system was maintained at 70 ℃ for 2 hours to conduct polymerization. The concentration was adjusted to 20% with ion-exchanged water to obtain a reaction mixture. The reaction mixture was analyzed by Gel Permeation Chromatography (GPC), and as a result, the mass average molecular weight was 298000. The reaction mixture was used as copolymer (PCA-1).
Synthesis of copolymer (PCA-2)
In a 1000mL round bottom flask equipped with a stirring blade, a stirrer, a nitrogen introduction tube, and a dropping funnel, 436.8g of ion exchange water, 338.9g of α -methacryloyl- ω -methoxy-poly (n = 23) oxyethylene, 59.6g of methacrylic acid, 0.4g of 3-mercaptopropionic acid, and 1.1g of octadecylthiol were placed, and the mixture was uniformly dissolved with stirring, and then the atmosphere was replaced with nitrogen gas, and the temperature of the reaction system was adjusted to 70 ℃ by a hot water bath. Next, a solution of 2.4g of 35% hydrogen peroxide water diluted with 35.8g of ion-exchanged water was added to the reaction system to start the polymerization reaction. The temperature of the reaction system was maintained at 70 ℃ for 2 hours to conduct polymerization. Then, a solution prepared by diluting 0.8g of 35% hydrogen peroxide water with 11.9g of ion-exchanged water was further added to the reaction system, and the temperature of the reaction system was maintained at 70 ℃ for 2 hours to conduct polymerization. The concentration was adjusted to 20% with ion-exchanged water to obtain a reaction mixture. The reaction mixture was analyzed by Gel Permeation Chromatography (GPC), and as a result, the mass average molecular weight was 277000. The reaction mixture was taken as a copolymer (PCA-2).
Synthesis of copolymer (PCA-3)
In a 1000mL round bottom flask equipped with a stirring blade, a stirrer, a nitrogen introduction tube, and a dropping funnel, 218.4g of ion exchange water, 159.2g of α -methacryloyl- ω -methoxy-poly (n = 45) oxyethylene, 39.8g of methacrylic acid, 0.08g of thioglycolic acid, and 0.40g of n-dodecylmercaptan were placed, and uniformly dissolved while stirring, and then the atmosphere was replaced with nitrogen gas, and the temperature of the reaction system was adjusted to 70 ℃ by passing through a hot water bath. Next, a solution prepared by diluting 1.2g of sodium persulfate with 18.0g of ion-exchanged water was added to the reaction system, and the polymerization reaction was started. The temperature of the reaction system was maintained at 70 ℃ for 2 hours to conduct polymerization. Then, a solution prepared by diluting 0.4g of sodium persulfate with 6.0g of ion-exchanged water was further added to the reaction system, and the temperature of the reaction system was maintained at 70 ℃ for 2 hours to carry out a polymerization reaction. The concentration was adjusted to 20% with ion-exchanged water to obtain a reaction mixture. The reaction mixture was analyzed by Gel Permeation Chromatography (GPC), and as a result, the mass average molecular weight was 350000. The reaction mixture was taken as copolymer (PCA-3).
Synthesis of copolymer (PCA-4)
In a 1000mL round-bottomed flask equipped with a stirrer, a nitrogen inlet tube, and a dropping funnel, 216.4g of ion-exchanged water and 153.8g of α - (3-methyl-3-butenyl) - ω -hydroxy-poly (n = 53) oxyethylene were uniformly dissolved while stirring, and then the atmosphere was replaced with nitrogen gas, and the temperature of the reaction system was adjusted to 70 ℃ by passing through a hot water bath. 45.2g of acrylic acid, 0.05g of a mixture of thioglycolic acid and 0.47g of hexadecylmercaptan, 3 hours, 16.0g of 3.5% hydrogen peroxide, and 4 hours, respectively, were added dropwise to the reaction system simultaneously with a solution prepared by diluting 1.3g of L-ascorbic acid with 11.7g of ion-exchanged water, thereby carrying out polymerization reaction. After completion of all the dropwise addition, the temperature was maintained at 70 ℃ for 1 hour. After cooling, the concentration was adjusted to 20% with ion-exchanged water to obtain a reaction mixture. The reaction mixture was analyzed by Gel Permeation Chromatography (GPC), and as a result, the mass average molecular weight was 250000. The reaction mixture was taken as copolymer (PCA-4).
Synthesis of copolymer (PCA-5)
In a 1000mL round-bottomed flask equipped with a stirrer, a nitrogen introduction tube, and a dropping funnel, 218.5g of ion-exchanged water and 126.8g of α -methallyl- ω -hydroxy-oxypropylene poly (n = 68) oxyethylene were uniformly dissolved while stirring, and then the atmosphere was replaced with nitrogen gas, and the temperature of the reaction system was adjusted to 70 ℃ by passing through a hot water bath. A mixture of 27.2g of hydroxyethyl acrylate, 27.2g of acrylic acid and 18.1g of methyl acrylate, a mixture of 0.18g of thioglycolic acid and 0.22g of 2-ethylhexyl mercaptan, a solution prepared by diluting 1.3g of L-ascorbic acid with 11.7g of ion-exchanged water, and the like were simultaneously added dropwise to the reaction system over 3 hours, 16.0g of 3.5% hydrogen peroxide and the like over 4 hours, respectively, to carry out polymerization reaction. After completion of the entire dropwise addition, the temperature was maintained at 70 ℃ for 1 hour to conduct polymerization. The concentration was adjusted to 20% with ion-exchanged water to obtain a reaction mixture. The reaction mixture was analyzed by Gel Permeation Chromatography (GPC), and as a result, the mass average molecular weight was 223000. The reaction mixture was taken as copolymer (PCA-5).
Synthesis of copolymer (PCA-6)
In a 1000mL round bottom flask equipped with a stirring blade, a stirrer, a nitrogen introduction tube, and a dropping funnel, 262.7g of ion-exchanged water, 208.5g of α -methacryloyl- ω -methoxy-poly (n = 113) oxyethylene, 31.2g of methacrylic acid, 0.14g of thioglycerol, and 0.19g of t-dodecylmercaptan were placed, and uniformly dissolved while stirring, then the atmosphere was replaced with nitrogen gas at a stirring speed of 200rpm, and the temperature of the reaction system was controlled to 70 ℃ by a hot water bath. Next, 23.0g of 2.2% hydrogen peroxide water was added to the reaction system to start the polymerization reaction. The temperature of the reaction system was maintained at 65 ℃ for 2 hours to conduct polymerization. Then, 7.7g of 2.2% hydrogen peroxide water was further added to the reaction system, and the temperature of the reaction system was maintained at 65 ℃ for 3 hours to conduct polymerization. The concentration was adjusted to 20% with ion-exchanged water to obtain a reaction mixture. The reaction mixture was analyzed by Gel Permeation Chromatography (GPC), and as a result, the mass average molecular weight was 358000. The reaction mixture was taken as copolymer (PCA-6).
Synthesis of copolymer (PCA-7)
Into a 1000mL round bottom flask equipped with a stirring blade, a stirrer, a nitrogen introduction tube, and a dropping funnel, 274.2g of ion exchange water, 191.7g of α -methacryloyl- ω -methoxy-poly (n = 9) oxyethylene, 43.1g of methacrylic acid, 0.20g of thioglycerol, 0.20g of n-dodecylmercaptan, and 4.8g of sodium allylsulfonate were placed, and the mixture was uniformly dissolved while stirring, and then the atmosphere was replaced with nitrogen gas, and the temperature of the reaction system was controlled to 80 ℃ by a hot water bath. Next, 14.4g of 3.5% hydrogen peroxide water was added to the reaction system to start the polymerization reaction. The temperature of the reaction system was maintained at 70 ℃ for 3 hours to conduct polymerization. Then, 4.8g of 3.5% hydrogen peroxide water was further added to the reaction system, and the temperature of the reaction system was maintained at 80 ℃ for 3 hours to effect polymerization. The concentration was adjusted to 20% with ion-exchanged water to obtain a reaction mixture. The reaction mixture was analyzed by Gel Permeation Chromatography (GPC), and as a result, the mass average molecular weight was 432000. The reaction mixture was taken as copolymer (PCA-7).
Synthesis of copolymer (PCA-8)
In a 1000mL round bottom flask equipped with a stirring blade, a stirrer, a nitrogen introduction tube, and a dropping funnel, 274.2g of ion exchange water, 179.4g of α -methacryloyl- ω -methoxy-poly (n = 45) oxyethylene, 43.1g of methacrylic acid, 16.7g of mono (2-acryloyloxyethyl) succinate, 0.14g of 3-mercaptopropionic acid, and 0.65g of n-dodecylmercaptan were placed, and the atmosphere was uniformly dissolved with stirring, then replaced with nitrogen gas, and the temperature of the reaction system was adjusted to 70 ℃ by a hot water bath. Next, 14.4g of 3.5% hydrogen peroxide water was added to the reaction system to start the polymerization reaction. The temperature of the reaction system was maintained at 70 ℃ for 3 hours to conduct polymerization. Then, 4.8g of 3.5% hydrogen peroxide water was further added to the reaction system, and the temperature of the reaction system was maintained at 70 ℃ for 3 hours to conduct polymerization. The concentration was adjusted to 20% with ion-exchanged water to obtain a reaction mixture. The reaction mixture was analyzed by Gel Permeation Chromatography (GPC), and as a result, the mass average molecular weight was 320000. The reaction mixture was taken as copolymer (PCA-8).
Synthesis of copolymer (PCA-9)
In a 1000mL round bottom flask equipped with a stirring blade, a stirrer, a nitrogen introduction tube and a dropping funnel, 274.2g of ion-exchanged water, 200.5g of α -methacryloyl- ω -methoxy-poly (n = 23) oxyethylene, 14.3g of methacrylic acid, 0.10g of thioglycolic acid, 1.17g of behenyl thiol, and 23.9g of methyl acrylate were placed, and the mixture was uniformly dissolved while stirring, then the atmosphere was replaced with nitrogen gas at a stirring speed of 200rpm, and the temperature of the reaction system was adjusted to 65 ℃ by a hot water bath. Next, 14.3g of 3.5% hydrogen peroxide water was added to the reaction system to start the polymerization reaction. The temperature of the reaction system was maintained at 65 ℃ for 4 hours to conduct polymerization. Then, 4.8g of 3.5% hydrogen peroxide water was further added to the reaction system, and the temperature of the reaction system was maintained at 70 ℃ for 2 hours to conduct polymerization. The concentration was adjusted to 20% with ion-exchanged water to obtain a reaction mixture. The reaction mixture was analyzed by Gel Permeation Chromatography (GPC), and as a result, the mass average molecular weight was 354000. The reaction mixture was taken as copolymer (PCA-9).
Synthesis of copolymer (PCA-10)
In a 1000mL round-bottomed flask equipped with a stirring blade, a stirrer, a nitrogen introduction tube, and a dropping funnel, 274.2g of ion-exchanged water, 210.2g of α -methacryloyl- ω -methoxy-poly (n = 45) oxyethylene, 28.8g of methacrylic acid, and 0.36g of 3-mercaptopropionic acid were placed, and uniformly dissolved while stirring, and then the atmosphere was replaced with nitrogen gas, and the temperature of the reaction system was set to 70 ℃ by passing through a hot water bath. Next, 14.4g of 3.5% hydrogen peroxide water was added to the reaction system to start the polymerization reaction. The temperature of the reaction system was maintained at 70 ℃ for 2 hours to conduct polymerization. Then, 4.8g of 3.5% hydrogen peroxide water was further added to the reaction system, and the temperature of the reaction system was maintained at 70 ℃ for 2 hours to effect polymerization. The concentration was adjusted to 20% with ion-exchanged water to obtain a reaction mixture. The reaction mixture was analyzed by Gel Permeation Chromatography (GPC), and as a result, the mass average molecular weight was 200000. The reaction mixture was taken as a copolymer (PCA-10).
Synthesis of copolymer (PCA-11)
In a 1000mL round bottom flask equipped with a stirring blade, a stirrer, a nitrogen introduction tube, and a dropping funnel, 274.3g of ion exchange water, 214.1g of α -methacryloyl- ω -methoxy-poly (n = 45) oxyethylene, 23.8g of methacrylic acid, 1.19g of 3-mercaptopropionic acid, and 0.90g of n-dodecylmercaptan were placed, and the mixture was uniformly dissolved while stirring, and then the atmosphere was replaced with nitrogen gas, and the temperature of the reaction system was adjusted to 70 ℃ by a hot water bath. Next, 14.3g of 3.5% hydrogen peroxide water was added to the reaction system to start the polymerization reaction. The temperature of the reaction system was maintained at 70 ℃ for 2 hours to conduct polymerization. Then, 4.8g of 3.5% hydrogen peroxide water was further added to the reaction system, and the temperature of the reaction system was maintained at 70 ℃ for 2 hours to conduct polymerization. The concentration was adjusted to 20% with ion-exchanged water to obtain a reaction mixture. The reaction mixture was analyzed by Gel Permeation Chromatography (GPC), and as a result, the mass average molecular weight was 80000. The reaction mixture was taken as a copolymer (PCA-11).
The mass average molecular weights of the synthesized copolymers (PCA-1) to (PCA-11) were measured by Gel Permeation Chromatography (GPC) under the following measurement conditions.
[ measurement conditions ]
The device comprises the following steps: shodex GPC-101 (manufactured by Showa electrician Co., ltd.)
Column: ohapak SB-G + SB-806M HQ + SB-806M HQ (made by SHO AND electrician Bingquan)
A detector: differential Refractometer (RI)
Eluent: 50mM aqueous sodium nitrate solution
Flow rate: 0.7 mL/min
Column temperature: 40 deg.C
Sample concentration: eluent solution with sample concentration of 0.5 wt%
Standard substance: polyethylene glycol polyethylene oxide (アジレント, テクノロジー, manufactured by Ski Co., ltd.)
Water was removed from the synthesized copolymers (PCA-1) to (PCA-11), and the solution was adjusted to a concentration of 5% using heavy water and determined by 1H-NMR at 300 MHz.
[ measurement conditions ]
The device comprises the following steps: varian Mercury 300 (アジレント. テクノロジー manufactured by Kyoto Co., ltd.)
And (3) determination of a solvent: heavy water
Measuring temperature: 20 deg.C
The contents of the respective copolymers and the measurement results are summarized and shown in table 1.
[ Table 1]
In the context of table 1, the following,
l-1: alpha-methacryloyl-omega-methoxy-poly (n = 45) oxyethylene
L-2: alpha-methacryloyl-omega-methoxy-poly (n = 23) oxyethylene
L-3: α -methacryloyl- ω -methoxy-poly (n = 113) oxyethylene
L-4: α - (3-methyl-3-butenyl) - ω -hydroxy-poly (n = 53) oxyethylene
L-5: alpha-methallyl-omega-hydroxy-oxypropylene poly (n = 68) oxyethylene
L-6: acrylic acid hydroxyethyl ester
L-7: alpha-methacryloyl-omega-methoxy-poly (n = 9) oxyethylene
M-1: methacrylic acid
M-2: acrylic acid
M-3: succinic acid mono (2-acryloyloxyethyl) ester
N-1: acrylic acid methyl ester
N-2: sodium allylsulfonate
TA-1: 3-mercaptopropionic acid
TA-2: thioglycollic acid
TA-3: thioglycerol
TB-1: n-dodecyl mercaptan
TB-2: octadecyl mercaptan
TB-3: hexadecyl mercaptan
TB-4: 2-ethylhexyl mercaptan
TB-5: tert-dodecyl mercaptan
TB-6: behenyl mercaptan
Test class 2 (Synthesis of copolymer (B))
Synthesis of the copolymer (PCB-1)
In a 1000mL round bottom flask equipped with a stirrer, a nitrogen inlet tube, and a dropping funnel, 170.0g of ion-exchanged water, 168.0g of α -methacryloyl- ω -methoxy-poly (n = 23) oxyethylene, 22.9g of methacrylic acid, and 1.7g of 3-mercaptopropionic acid were placed, and uniformly dissolved while stirring, and then the atmosphere was replaced with nitrogen gas, and the temperature of the reaction system was adjusted to 60 ℃ by a hot water bath. Next, a solution of 2.8g of sodium persulfate diluted with 42.1g of ion-exchanged water was added to the reaction system to start the polymerization reaction. The temperature of the reaction system was maintained at 60 ℃ for 2 hours to conduct polymerization. Then, a solution prepared by diluting 0.9g of sodium persulfate with 14.0g of ion-exchanged water was further added to the reaction system, and the temperature of the reaction system was maintained at 60 ℃ for 2 hours to conduct polymerization. The reaction mixture was adjusted to pH6 using a 30% aqueous sodium hydroxide solution, and further adjusted to a concentration of 20% with ion-exchanged water. The reaction mixture was analyzed by Gel Permeation Chromatography (GPC), and as a result, the mass average molecular weight was 24000. The reaction mixture was used as a copolymer (PCB-1).
Synthesis of copolymer (PCB-2)
Into a round-bottomed flask were placed 171.2g of ion-exchanged water, 168.0g of α -methacryloyl- ω -methoxy-poly (n = 45) oxyethylene, 21.0g of methacrylic acid, 1.9g of methyl acrylate, 1.8g of thioglycolic acid, and 20.5g of a 30% aqueous sodium hydroxide solution, and the mixture was uniformly dissolved with stirring, and then the atmosphere was replaced with nitrogen gas, and the temperature was brought to 65 ℃ by passing through a hot water bath. Next, a solution prepared by diluting 2.8g of ammonium persulfate with 42.1g of ion-exchanged water was added to the reaction system, and the polymerization reaction was started. The temperature of the reaction system was maintained at 65 ℃ for 3 hours to conduct polymerization. Then, a solution prepared by diluting 0.9g of ammonium persulfate with 14.0g of ion-exchanged water was further added to the reaction system, and the temperature of the reaction system was maintained at 65 ℃ for 2 hours to carry out a polymerization reaction. The reaction mixture was adjusted to pH7 using a 30% aqueous sodium hydroxide solution, and further adjusted to a concentration of 20% with ion-exchanged water. The reaction mixture was analyzed by Gel Permeation Chromatography (GPC), and as a result, the mass average molecular weight was 28000. The reaction mixture was used as a copolymer (PCB-2).
Synthesis of copolymer (PCB-3)
A1000 mL round-bottomed flask equipped with a stirrer, a nitrogen inlet tube and a dropping funnel was charged with 133.5g of ion-exchanged water, the atmosphere was replaced with nitrogen gas, and the temperature of the reaction system was adjusted to 70 ℃ by passing through a hot water bath. A solution obtained by uniformly stirring 175.4g of α -methacryloyl- ω -methoxy-poly (n = 113) oxyethylene, 15.3g of methacrylic acid, and 1.5g of 3-mercaptopropionic acid was added dropwise to the reaction system over 3 hours. Further, a solution of 3.0g of 35% hydrogen peroxide water diluted with 52.0g of ion-exchanged water was simultaneously dropped into the reaction system over 4 hours, and after the entire solution was dropped, the temperature of the reaction system was maintained at 70 ℃ for 1 hour. After completion of the reaction, the reaction mixture was adjusted to pH6 using a 30% aqueous sodium hydroxide solution, and further adjusted to a concentration of 20% with ion-exchanged water. The reaction mixture was analyzed by Gel Permeation Chromatography (GPC), and as a result, the mass average molecular weight was 34000. The reaction mixture was used as a copolymer (PCB-3).
Synthesis of copolymer (PCB-4)
In a 1000mL round-bottomed flask equipped with a stirrer, a nitrogen introduction tube, and a dropping funnel, 102.6g of ion-exchanged water and 180.6g of α - (3-methyl-3-butenyl) - ω -hydroxy-poly (n = 53) oxyethylene were placed, and uniformly dissolved while stirring, and then the atmosphere was replaced with nitrogen gas, and the temperature of the reaction system was adjusted to 65 ℃ by passing through a hot water bath. A solution prepared by diluting 15.7g of acrylic acid with 76.5g of ion-exchanged water was added dropwise over 3 hours, 9.8g of 3.5% hydrogen peroxide water was added dropwise to the reaction system over 3 hours, and a solution prepared by diluting 0.8g of 3-mercaptopropionic acid with 0.8g of L-ascorbic acid with 6.3g of ion-exchanged water was added dropwise to the reaction system over 4 hours. Further, the temperature of the reaction system was maintained at 65 ℃ for 1 hour to effect aging. The reaction mixture was adjusted to pH5 using a 30% aqueous sodium hydroxide solution and adjusted to a concentration of 20% with ion-exchanged water. The reaction mixture was analyzed by Gel Permeation Chromatography (GPC), and as a result, the mass average molecular weight was 36000. The reaction mixture was used as a copolymer (PCB-4).
Synthesis of the copolymer (PCB-5)
In a 1000mL round bottom flask equipped with a stirrer, a nitrogen inlet tube and a dropping funnel, 151.0g of ion exchange water and 177.0g of α -methallyl- ω -hydroxy-oxypropylene poly (n = 68) oxyethylene were placed, and uniformly dissolved with stirring, and then the atmosphere was replaced with nitrogen gas, and the temperature of the reaction system was adjusted to 60 ℃ by passing through a hot water bath. A solution of 11.8g of acrylic acid and 7.9g of hydroxyethyl acrylate diluted with 31.5g of ion-exchanged water was added dropwise over 3 hours, while 8.9g of 3.5% hydrogen peroxide water was added dropwise to the reaction system over 3 hours, and a solution of 1.0g of 3-mercaptopropionic acid diluted with 7.1g of ion-exchanged water and 0.8g of L-ascorbic acid was added dropwise to the reaction system over 4 hours. Further, the temperature of the reaction system was maintained at 60 ℃ for 0.5 hour to effect aging. The reaction mixture was adjusted to pH7 using a 30% aqueous sodium hydroxide solution and adjusted to a concentration of 20% with ion-exchanged water. The reaction mixture was analyzed by Gel Permeation Chromatography (GPC), and as a result, the mass average molecular weight was 39000. The reaction mixture was used as a copolymer (PCB-5).
The mass average molecular weights of the synthesized copolymers (PCB-1) to (PCB-5) were measured by gel permeation chromatography under the same measurement conditions as for the copolymers (PCA-1) to (PCA-11).
The synthesized copolymers (PCB-1) to (PCB-5) were measured by 1H-NMR at 300MHz in the same manner as the copolymers (PCA-1) to (PCA-11).
The contents of the respective copolymers and the measurement results are summarized and shown in table 2.
[ Table 2]
Test class 3 (preparation of additive for Hydraulic composition)
Preparation of additives (EX-1 to EX-14) for Hydraulic compositions
Under the formulation conditions described in table 3, the copolymer (a) and the copolymer (B) were mixed to prepare an additive for hydraulic compositions.
[ Table 3]
* Sodium gluconate reagent
Test type 4 (preparation and evaluation of Hydraulic composition)
Examples 1 to 14 and comparative examples 1 to 3
The additives for hydraulic compositions shown in Table 3 were evaluated based on hydraulic compositions. The hydraulic compositions of the test examples shown in table 5 were prepared as follows under the formulation conditions shown in table 4. Ordinary portland cement (made by pacific cement corporation, mitsubishi cement corporation, sumitomo osaka cement corporation) was mixed in equal amounts in a test room at 20 ℃ so as to have a density =3.16g/cm in predetermined amounts, respectively 3 ) Broken sand (rock-washed and sand-made garrulous sand, density =2.64 g/cm) 3 ) Crushed stone (crushed stone produced by Okazaki, density =2.66 g/cm) 3 ) Was charged into a 50L forced double shaft mixer, and was charged with kneading water (tap water) so that the aliphatic polyether defoamer (trade name AFK-2 manufactured by bamboo oil and fat Co., ltd.) was in a proportion of 0.005% to the cement, and kneaded for 90 secondsThe amounts of additives for hydraulic compositions and air quantity regulators (trade name AE-300 manufactured by bamboo fat and oil Co., ltd.) were adjusted so that the slump was within the range of 18. + -. 1cm and the air quantity was within the range of 4.5. + -. 0.5%.
[ Table 4]
Evaluation of Hydraulic composition
The slump, air quantity, compressive strength and bleeding amount of each of the prepared hydraulic compositions were determined as follows. The results are summarized and shown in table 5.
Slump (cm): the air quantity was measured in accordance with JIS-A1101.
Air amount (% by volume): the hydraulic composition immediately after kneading and after leaving for 30 minutes was measured in accordance with JIS-A1128.
Compressive strength: the age of a cured product obtained by curing the hydraulic composition of each example using a die having a diameter of 100mm and a height of 200mm was measured in accordance with JIS-A1108.
Amount of exudation: the hydraulic composition immediately after kneading was measured in accordance with JIS-A1123.
[ Table 5]
(results)
In examples 1 to 14, it was confirmed that by using the additive for hydraulic compositions containing the copolymer (a), bleeding was reduced while maintaining dispersibility, slump retention property, and separation resistance of the hydraulic composition, as compared with comparative examples 1 to 3.
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 copolymer (A) and the following copolymer (B),
the mass average molecular weight Ma of the copolymer (A) and the mass average molecular weight Mb of the copolymer (B) satisfy the following relational expression:
Ma-Mb≥ 80000
copolymer (a): a copolymer which has a structure derived from a vinyl monomer comprising a structural unit (1) and a structural unit (2), has a structure derived from a hydrophobic chain transfer agent comprising a sulfur atom, and has a mass average molecular weight of 100000 to 2000000 as measured by gel permeation chromatography in terms of polyethylene glycol,
structural unit (1): a structural unit formed by one or more monomers selected from the group represented by the following general formula 1,
structural unit (2): a structural unit formed from an unsaturated carboxylic acid and/or a salt thereof, wherein 80 to 100 mol% of the unsaturated carboxylic acid and/or a salt thereof is formed from one or two or more selected from (meth) acrylic acid and/or a salt thereof,
[ chemical formula 1]
Wherein, in the formula, R 1 、R 2 And R 3 Identical or different, represent a hydrogen atom or a methyl group; r is 4 The same or different, represents hydrogen or a hydrocarbon group having 1 to 30 carbon atoms; p represents an integer of 0 or 1; q represents an integer of 0 to 2; AO represents an oxyalkylene group having 2 to 18 carbon atoms; n is the average molar number of addition of AO and represents a value of 1 to 300,
copolymer (B): a copolymer having a structure derived from a vinyl monomer containing the structural unit (1) and the structural unit (2), and having a mass average molecular weight in terms of polyethylene glycol as measured by gel permeation chromatography of 5000 or more and less than 100000.
2. The additive for hydraulic compositions according to claim 1, which has the following structure: the structure derived from the hydrophobic chain transfer agent has an alkyl chain, and at least one terminal of the structure derived from the hydrophobic chain transfer agent is bonded to a terminal of a main chain of the structure derived from the vinyl monomer via a sulfur atom.
3. The additive for hydraulic compositions according to claim 1, wherein the mass average molecular weight of the copolymer (A) is 100000 to 600000.
4. The additive for hydraulic compositions according to claim 2, wherein the number of carbon atoms in the alkyl chain is 8 to 22.
5. The additive for hydraulic compositions according to claim 1, wherein the mass ratio of the structural unit (2) to the structural unit (1) is structural unit (2)/structural unit (1) =30/70 to 1/99.
6. The additive for hydraulic compositions according to claim 1, wherein the mass ratio of the copolymer (A) to the copolymer (B) is copolymer (A)/copolymer (B) =1/99 to 30/70.
7. A hydraulic composition comprising the additive for hydraulic compositions according to claim 1.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1103570A2 (en) * | 1999-11-29 | 2001-05-30 | Nippon Shokubai Co., Ltd. | Copolymer for cement admixtures and its production process and use |
| CN1890193A (en) * | 2004-01-06 | 2007-01-03 | 株式会社日本触媒 | Cement admixture |
| JP2007076972A (en) * | 2005-09-15 | 2007-03-29 | Hokkaido Univ | Self shrinkage-reducing agent |
| TW201311605A (en) * | 2011-09-12 | 2013-03-16 | Nippon Catalytic Chem Ind | Poly(carboxylic acid)-based polymer for hydraulic material additive |
| CN105712652A (en) * | 2015-12-15 | 2016-06-29 | 江苏苏博特新材料股份有限公司 | Slump loss resistant agent for concrete with medium and low slump and preparation method of slump loss resistant agent |
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| JP3992492B2 (en) * | 2000-12-27 | 2007-10-17 | 株式会社日本触媒 | Polycarboxylic acid copolymer, method for producing the same, and use thereof |
| JP2006306663A (en) * | 2005-04-28 | 2006-11-09 | Nippon Shokubai Co Ltd | Dispersant for self-leveling material |
| JP6819321B2 (en) * | 2017-01-30 | 2021-01-27 | 日本製紙株式会社 | A method for producing a cement composition. |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| EP1103570A2 (en) * | 1999-11-29 | 2001-05-30 | Nippon Shokubai Co., Ltd. | Copolymer for cement admixtures and its production process and use |
| CN1890193A (en) * | 2004-01-06 | 2007-01-03 | 株式会社日本触媒 | Cement admixture |
| JP2007076972A (en) * | 2005-09-15 | 2007-03-29 | Hokkaido Univ | Self shrinkage-reducing agent |
| TW201311605A (en) * | 2011-09-12 | 2013-03-16 | Nippon Catalytic Chem Ind | Poly(carboxylic acid)-based polymer for hydraulic material additive |
| CN105712652A (en) * | 2015-12-15 | 2016-06-29 | 江苏苏博特新材料股份有限公司 | Slump loss resistant agent for concrete with medium and low slump and preparation method of slump loss resistant agent |
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