CN111051265B - Dispersion maintaining agent for hydraulic composition - Google Patents
Dispersion maintaining agent for hydraulic composition Download PDFInfo
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- CN111051265B CN111051265B CN201780094648.1A CN201780094648A CN111051265B CN 111051265 B CN111051265 B CN 111051265B CN 201780094648 A CN201780094648 A CN 201780094648A CN 111051265 B CN111051265 B CN 111051265B
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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
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F216/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal or ketal radical
- C08F216/12—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal or ketal radical by an ether radical
- C08F216/14—Monomers containing only one unsaturated aliphatic radical
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/20—Esters of polyhydric alcohols or phenols, e.g. 2-hydroxyethyl (meth)acrylate or glycerol mono-(meth)acrylate
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/26—Esters containing oxygen in addition to the carboxy oxygen
- C08F220/28—Esters containing oxygen in addition to the carboxy oxygen containing no aromatic rings in the alcohol moiety
- C08F220/285—Esters containing oxygen in addition to the carboxy oxygen containing no aromatic rings in the alcohol moiety and containing a polyether chain in the alcohol moiety
- C08F220/286—Esters containing oxygen in addition to the carboxy oxygen containing no aromatic rings in the alcohol moiety and containing a polyether chain in the alcohol moiety and containing polyethylene oxide in the alcohol moiety, e.g. methoxy polyethylene glycol (meth)acrylate
Abstract
The invention provides a dispersion retention agent for hydraulic compositions, which can retain the fluidity of hydraulic compositions and has little hardening delay even after a long time after kneading. As the dispersion-retaining agent for hydraulic compositions, a vinyl copolymer obtained by copolymerizing a specific monomer having a carboxyl group in the molecule, a specific monomer having a polyalkylene glycol residue in the molecule, and if necessary, another monomer copolymerizable with these monomers is used.
Description
Technical Field
The present invention relates to a dispersion maintaining agent for hydraulic compositions. Various dispersants are widely used for the production of hydraulic compositions such as mortar and concrete. However, when a hydraulic composition is produced using a dispersant, slump loss (decrease in fluidity with time) is generally increased, and workability are reduced. The present invention relates to a dispersion maintaining agent for hydraulic compositions, which can sufficiently prevent slump loss.
Background
Conventionally, as a preparation having slump loss prevention performance, a dispersant for hydraulic compositions comprising a water-soluble vinyl copolymer has been proposed (for example, see patent documents 1 to 4). However, these conventional proposals have a problem that slump loss of the prepared hydraulic composition cannot be sufficiently prevented. Therefore, there has been proposed a slump loss inhibitor used in combination with a dispersant for hydraulic compositions (see, for example, patent document 5). However, this conventional proposal still has a problem that slump loss of the produced hydraulic composition cannot be sufficiently prevented.
Patent document 1: japanese laid-open patent publication No. 63-285140
Patent document 2: japanese laid-open patent publication No. 1-226757
Patent document 3: japanese laid-open patent publication No. 10-67549
Patent document 4: japanese patent laid-open publication No. 2003-335562
Patent document 5: japanese patent laid-open publication No. 2003-34565
Disclosure of Invention
Problems to be solved by the invention
The present invention addresses the problem of providing a dispersion-retaining agent for hydraulic compositions, with which the fluidity of hydraulic compositions can be retained even after a long period of time has elapsed after kneading, and with which the delay in curing is small.
Means for solving the problems
The present inventors have made studies to solve the above problems, and as a result, have found that a vinyl copolymer obtained by copolymerizing a specific monomer having a carboxyl group in the molecule, a specific monomer having a polyalkylene glycol residue in the molecule, and if necessary, another monomer copolymerizable with these monomers is suitable as a dispersion maintaining agent for a hydraulic composition.
That is, the present invention relates to a dispersion maintaining agent for a hydraulic composition, which is characterized by containing a vinyl copolymer obtained from a monomer a represented by the following chemical formula 1 and a monomer B represented by the following chemical formula 2. The present invention also relates to a dispersion maintaining agent for hydraulic compositions, which is characterized by containing a vinyl copolymer obtained from a monomer A represented by the following chemical formula 1, a monomer B represented by the following chemical formula 2, and another monomer C copolymerizable with these monomers.
[ chemical formula 1]
[ chemical formula 2]
In chemical formula 1 and chemical formula 2,
R1、R2: a hydrogen atom, a methyl group or a group represented by the following chemical formula 3Organic group of (2)
p: 0 or 1
X: an organic group represented by the following chemical formula 4
Y: an organic group represented by the following chemical formula 5
M1: hydrogen atom, ammonium group, organic amine group, alkali metal or 1/2 equivalent of alkaline earth metal
[ chemical formula 3]
-(CH2)r-COOM2
In chemical formula 3, r: 0 or 1
M2: hydrogen atom, ammonium group, organic amine group, alkali metal or 1/2 equivalent of alkaline earth metal
[ chemical formula 4]
-(AO)m-R3-
In the chemical formula 4, the first and second,
AO: alkylene oxide having 2 to 4 carbon atoms
m: 1 to 10 in total
R3: alkylene, aromatic ring, or unsaturated hydrocarbon radicals, with or without hetero atoms
[ chemical formula 5]
-(CH2)s(CO)tO(AO)n-R4
In the chemical formula 5, the first and second,
s: an integer of 0 to 4
t: 0 or 1
AO: alkylene oxide having 2 to 4 carbon atoms
n: an integer of 0 to 300
R4: a hydrogen atom, an alkyl group having 1 to 22 carbon atoms or an aliphatic acyl group having 1 to 22 carbon atoms (wherein, when n is 0, R is4Is an alkyl group having 1 to 22 carbon atoms or an aliphatic acyl group having 1 to 22 carbon atoms)
The dispersion-retaining agent for a hydraulic composition of the present invention (hereinafter referred to as the dispersion-retaining agent of the present invention) comprises: a dispersion maintaining agent containing a vinyl copolymer (hereinafter referred to as a vinyl copolymer P) obtained from a monomer a represented by the above chemical formula 1 and a monomer B represented by the above chemical formula 2; and a dispersion-retaining agent comprising a vinyl copolymer (hereinafter referred to as a vinyl copolymer Q) obtained from the monomer A, the monomer B, and another monomer C copolymerizable therewith.
First, the vinyl copolymer P will be explained. The vinyl copolymer P is a vinyl copolymer obtained from the monomer a and the monomer B, and the ratio of the two is not particularly limited, and the following vinyl copolymer is preferable: the monomer A-derived structural unit is contained in an amount of 1 to 99 mol% and the monomer B-derived structural unit is contained in an amount of 1 to 99 mol% (total 100 mol%) in the total structural units, and the mass average molecular weight is 8000 to 200000.
In the above chemical formula 1, R represents a monomer A1Is a hydrogen atom, a methyl group or an organic group represented by the above chemical formula 3, p is 0 or 1, X is an organic group represented by the above chemical formula 4, M1Hydrogen atoms, ammonium groups, organic amine groups, alkali metals or 1/2 equivalents of alkaline earth metals. In chemical formula 3, r is 0 or 1, M2The organic group represented by chemical formula 3 is specifically a carboxyl group or a methylene carboxyl group, and is hydrogen atom, an ammonium group, an organic amine group, an alkali metal or 1/2 equivalents of an alkaline earth metal.
In chemical formula 4, AO represents an oxyalkylene group having 2 to 4 carbon atoms, m represents an integer of 1 to 10, and R represents3Is alkylene with or without hetero atoms, aromatic cyclic group or unsaturated hydrocarbon.
In chemical formula 4, the oxyalkylene group of AO includes oxyethylene group, oxypropylene group and oxybutylene group, preferably oxyethylene group and oxypropylene group, and more preferably oxyethylene group. These groups may be 1 kind or 2 or more kinds. m is an integer of 1 to 10, preferably an integer of 1 to 5, more preferably 1 or 2. R3Is an alkylene group, an aromatic ring group or an unsaturated hydrocarbon group, with or without a hetero atom, and the number of carbon atoms of these groups is not particularly limited. Examples of the alkylene group having or not having a hetero atom include a methylene group, an ethylene group, a propylene group, a butylene group, a cyclohexyl group, an oxymethylene group, an oxyethylene group, an oxypropylene group, and an oxybutylene group. In addition, as having or not having hetero atomsExamples of the aromatic ring group in (b) include phenylene, tolylene, naphthylene, thiophene, furan, pyrrole, benzothiophene, benzofuran, benzopyrrole, triazine, imidazole, benzimidazole, triazole, thiadiazole, and thiazole. Further, examples of the unsaturated hydrocarbon group having or not having a hetero atom include an ethynyl group, a propynyl group, a butynyl group, and a group having a carbonyl group or an imino group before or after these groups, and an organic group represented by the following chemical formula 6 is preferable.
[ chemical formula 6]
In chemical formula 6, R5Is an alkylene group having 1 to 22 carbon atoms, an aromatic ring group or an unsaturated hydrocarbon group, with or without a hetero atom, u is an integer of 0 to 2, M3Hydrogen atoms, organic ammonium groups, organic groups, alkali metals or 1/2 equivalents of alkaline earth metals.
In chemical formula 6, R5Is an alkylene group, aromatic group or unsaturated hydrocarbon group having 1 to 22 carbon atoms with or without a hetero atom, and R is as described above for R of chemical formula 4 with respect to the alkylene group, aromatic ring group or unsaturated hydrocarbon group with or without a hetero atom3Said, but R5Among them, those having 1 to 22 carbon atoms are preferable, and those having 1 to 6 carbon atoms are preferable.
In chemical formula 1, chemical formula 3, chemical formula 6, M1、M2、M3Hydrogen atoms, ammonium groups, organic amine groups, alkali metals or 1/2 equivalents of alkaline earth metals. These may be 1 kind or 2 or more kinds. Examples of the ammonium group include an ammonium group, a tetramethylammonium group, and a tetrabutylammonium group. Examples of the organic amine group include an alkylamino group such as a methylamino group, a dimethylamino group, a trimethylamine group, or a triethylamine group, an alkanolamide group such as a diethanolamide group or a triethanolamide group, an aromatic amine group such as a pyridinium group or a dimethylpyridinium group. Further, examples of the alkali metal include lithium, sodium, potassium, cesium, and the like. The alkaline earth metal includes calcium, magnesium, barium, and the like. In which case of alkaline earth metalsIn this case 1/2 equivalents.
Specific examples of the monomer A described above include 2-acryloyloxyethylsuccinic acid, 2-methacryloyloxyethylsuccinic acid, 2-acryloyloxyethylhexahydrophthalic acid, 2-acryloyloxyethylphthalic acid and the like, and further include condensates of an unsaturated carboxylic acid ester having a hydroxyl group at the terminal, such as hydroxyethyl (meth) acrylate and polyoxyethylene mono (meth) acrylate, and a 2-to 4-membered carboxylic acid anhydride. The condensation product is obtained by condensation of an unsaturated carboxylic acid ester having a hydroxyl group at the terminal and a 2-to 4-membered carboxylic acid anhydride. Examples of the unsaturated carboxylic acid ester that can be used for condensation include hydroxyethyl acrylate, hydroxyethyl methacrylate, hydroxypropyl acrylate, hydroxypropyl methacrylate, hydroxybutyl acrylate, hydroxybutyl methacrylate, polyoxyalkylene mono (meth) acrylate, and the like. Examples of the 2-to 4-membered carboxylic acid anhydride which can be used for condensation include succinic anhydride, maleic anhydride, trimellitic anhydride, cyclohexyl 1, 2-dicarboxylic anhydride, pyromellitic anhydride, and the like. As the monomer A, 1 or 2 or more of the above condensates can be used, and a condensate of hydroxyethyl (meth) acrylate and a 2-to 4-membered carboxylic acid anhydride is preferred.
The above condensate can be obtained by a known method. Among them are, for example, the following methods: a method of heating and stirring an unsaturated carboxylic acid ester having a hydroxyl group at the end and a 2-to 4-membered carboxylic acid anhydride in the absence of a solvent; a method of condensing an unsaturated carboxylic acid ester having a hydroxyl group at the terminal thereof with a 2-to 4-membered carboxylic acid anhydride in the presence of a solvent and a condensing agent; and so on.
In the above chemical formula 2 representing the monomer B, R2Is a hydrogen atom, a methyl group or an organic group represented by the above chemical formula 3, and Y is an organic group represented by the above chemical formula 5. In the chemical formula 5, s is an integer of 0 to 4, t is 0 or 1, AO is an oxyalkylene group having 2 to 4 carbon atoms, n is an integer of 0 to 300, R4Is a hydrogen atom, an alkyl group having 1 to 22 carbon atoms or an aliphatic acyl group having 1 to 22 carbon atoms. Wherein, when n is 0, R4Is an alkyl group having 1 to 22 carbon atoms or an aliphatic acyl group having 1 to 22 carbon atoms.
As R in chemical formula 54Can give an example of: 1) a hydrogen atom; 2) methyl, ethyl, butyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, eicosyl, heneicosyl, docosyl, tricosyl, tetracosyl, pentacosyl, hexacosyl, heptacosyl, octacosyl, 2-methyl-pentyl, 2-ethyl-hexyl, 2-propyl-heptyl, 2-butyl-octyl, 2-pentyl-nonyl, 2-hexyl-decyl, 2-heptyl-undecyl, 2-octyl-dodecyl, 2-nonyl-tridecyl, 2-decyl-tetradecyl, 2-undecyl-pentadecyl, decyl, dodecyl-decyl-tridecyl, 2-decyl-tetradecyl, 2-decyl-pentadecyl, dodecyl-benzyl, dodecyl-decyl-dodecyl-benzyl, dodecyl-benzyl-, An alkyl group having 1 to 22 carbon atoms such as 2-dodecyl-hexadecyl; 3) and aliphatic acyl groups having 1 to 22 carbon atoms such as formyl group, acetyl group, propionyl group, butyryl group, hexanoyl group, heptanoyl group, octanoyl group, nonanoyl group, decanoyl group, hexadecanoyl group, octadecanoyl group, hexadecanoyl group, eicosanoyl group, and octadecenoyl group. Wherein, as R4Preferably a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or an aliphatic acyl group having 1 to 4 carbon atoms.
As for AO in chemical formula 5, n is an integer of 0 to 300 as described above for AO in chemical formula 4, but As (AO) n, a (poly) oxyalkylene group composed of 0 to 160 oxyethylene units and/or oxypropylene units is preferable.
Specific examples of the monomer B described above include hydroxyethyl acrylate, hydroxyethyl methacrylate, propylhydroxy acrylate, propylhydroxy methacrylate, methyl acrylate, methyl methacrylate, propyl acrylate, propyl methacrylate, butyl acrylate, butyl methacrylate, α -allyl- ω -acetyl- (poly) ethylene oxide (poly) propylene oxide, α -allyl- ω -hydroxy- (poly) ethylene oxide (poly) propylene oxide, α -methallyl- ω -hydroxy- (poly) ethylene oxide, α -methallyl- ω -methoxy- (poly) ethylene oxide, propylene oxide, Alpha-methallyl-omega-hydroxy- (poly) oxyethylene (poly) oxypropylene, 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) oxyethylene (poly) oxypropylene, alpha-acryloyl-omega-hydroxy- (poly) oxyethylene, alpha-allyl-omega-hydroxy- (poly) oxyethylene, alpha-hydroxy-methyl-3-butenyl-oxy-ethylene, alpha-hydroxy-methyl-3-butenyl-hydroxy-ethylene, alpha-, α -acryloyl- ω -methoxy- (poly) ethylene oxide, α -acryloyl- ω -butoxy- (poly) ethylene oxide, α -acryloyl- ω -methoxy- (poly) ethylene oxide (poly) propylene oxide, α -methacryloyl- ω -hydroxy- (poly) ethylene oxide, α -methacryloyl- ω -methoxy- (poly) ethylene oxide, α -methacryloyl- ω -butoxy- (poly) ethylene oxide, α -acryloyl- ω -methoxy- (poly) ethylene oxide (poly) propylene oxide, α -methacryloyl- ω -hydroxy- (poly) ethylene oxide (poly) propylene oxide, α -methacryloyl- ω -acetyl- (poly) ethylene oxide (poly) propylene oxide, and the like.
The monomer B represented by chemical formula 2 may be 1 or 2 or more, preferably 2 or more, and among them, 2 monomers are preferably included when n in chemical formula 5 is 0 to 8 and 2 monomers are preferably included when n in chemical formula 5 is 9 to 160, and more specifically, 1 or 2 or more monomers B selected from hydroxyethyl acrylate, hydroxyethyl methacrylate, hydroxypropyl acrylate, hydroxypropyl methacrylate, methyl acrylate, methyl methacrylate, propyl acrylate, propyl methacrylate, butyl acrylate, butyl methacrylate, and other monomers B are preferably included.
Next, the vinyl copolymer Q will be described. The vinyl copolymer Q is obtained by copolymerizing the monomer a and the monomer B, and another monomer C copolymerizable therewith. Examples of the other monomer C include: 1) allylsulfonic acid, methallylsulfonic acid, alkali metal salts, alkaline earth metal salts, ammonium salts, amine salts thereof, and the like; 2) acrylic monomers such as acrylic acid, methacrylic acid, crotonic acid, maleic acid, fumaric acid, itaconic acid, and citraconic acid, and alkali metal salts, alkaline earth metal salts, ammonium salts, amine salts, methyl esters, ethyl esters, and acid anhydrides thereof; 3) (meth) acrylamide, N-methyl (meth) acrylamide, N-dimethyl (meth) acrylamide, 2- (meth) acrylamide-2-methanesulfonic acid, 2- (meth) acrylamide-2-ethanesulfonic acid, 2- (meth) acrylamide-2-propanesulfonic acid, styrene sulfonic acid; and so on. Among these, as the other monomer C, an acrylic monomer is preferable.
In the vinyl copolymers P and Q, the proportion of the monomer a in the total monomers used is preferably 1 to 99 mol%, more preferably 50 to 90 mol%. The proportion of the monomer B is preferably 1 to 99 mol%, more preferably 1 to 55 mol%. Further, the proportion of the other monomer C is preferably 50 mol% or less, more preferably 25 mol% or less, and particularly preferably 10 mol% or less.
The mass average molecular weights of the vinyl copolymers P and Q are preferably 8000 to 200000, more preferably 9000 to 150000, and particularly preferably 10000 to 100000. The mass average molecular weight in the present invention is a value in terms of polyethylene glycol based on gel permeation chromatography (hereinafter referred to as GPC).
The vinyl copolymers P and Q to be used in the dispersion retention agent of the present invention can be obtained by a known method. Examples thereof include radical polymerization using water as a solvent, radical polymerization using an organic solvent as a solvent, and radical polymerization without using a solvent. Examples of the radical polymerization initiator used in the radical polymerization include a polymerization initiator which generates radicals by decomposing at a polymerization reaction temperature, such as hydrogen peroxide, peroxides such as ammonium persulfate, sodium persulfate, and potassium persulfate, and azo compounds such as azobisisobutyronitrile, and also include a redox initiator used together with a reducing agent. A chain transfer agent may be used in order to set the mass average molecular weight of the resulting vinyl copolymer within a desired range. The chain transfer agent is not particularly limited as long as the molecular weight of the vinyl copolymer can be adjusted, and a known chain transfer agent can be used. Specifically, there may be mentioned: 1) thiol chain transfer agents such as mercaptoethanol, thioglycerol, thioglycolic acid, mercaptopropionic acid, 2-mercaptopropionic acid, 3-mercaptopropionic acid, thiomalic acid, octyl thioglycolate, octyl 3-mercaptopropionate, 2-mercaptoethanesulfonic acid, n-dodecylmercaptan, octylmercaptan, butyl thioglycolate, and the like; 2) halides such as carbon tetrachloride, carbon tetrabromide, methylene chloride, bromoform, bromotrichloroethane, and the like; 3) unsaturated hydrocarbon compounds such as α -methylstyrene dimer, α -terpinene, γ -terpinene, dipentene, terpinolene, etc.; 4) primary alcohols such as 2-aminopropane-1-ol and secondary alcohols such as isopropyl alcohol; 5) phosphorous acid, hypophosphorous acid, sodium hypophosphite, potassium hypophosphite, or the like, or a lower oxide or a salt thereof such as sulfurous acid, bisulfite (gamma-bisulfite), dithionous acid, pyrosulfurous acid, sodium sulfite, potassium sulfite, sodium bisulfite, potassium bisulfite, sodium dithionite, potassium dithionite, sodium metabisulfite, potassium metabisulfite, or the like; and so on. The vinyl copolymers P and Q can be obtained by anionic polymerization or cationic polymerization in addition to the above-described radical polymerization, and examples of the initiator used in these polymerizations include alkali metals, butyl lithium, grignard reagents, metal alkoxides, lewis acids such as boron trifluoride, bronsted acids such as sulfuric acid, and the like, and a method of radical polymerization in a solvent-free or water solvent is preferable.
The dispersion-retaining agent of the present invention is used as an admixture in the production of a hydraulic composition such as mortar or concrete, and can sufficiently prevent slump loss of mortar or concrete produced by using the same. The material used for the preparation of mortar and concrete is not particularly limited, and examples of the binder include: 1) various portland cements such as ordinary portland cement, early strength portland cement, moderate heat portland cement, and low heat portland cement; 2) various mixed cements such as blast furnace slag cement, fly ash cement, silica fume cement, and the like; 3) alumina cement; and so on. The water/binder ratio is not particularly limited, and is preferably 20 to 70%, more preferably 35 to 65%. Further, the kind of other dispersant used in the preparation of mortar or concrete is not particularly limited, and as the dispersant to be used in combination, one or two or more selected from hydroxycarboxylic acid or salt thereof, polycarboxylic acid-based or aromatic sulfonic acid-based dispersants are preferable. Additives such as AE agents, antifoaming agents, retarders, curing accelerators, shrinkage reducers and thickeners can be used for the preparation of mortar or concrete. The amount of the dispersion-retaining agent of the present invention is not particularly limited, and is usually 0.005 to 1.0 part by mass, preferably 0.005 to 0.5 part by mass, and more preferably 0.01 to 0.5 part by mass in terms of solid content, based on 100 parts by mass of the binder.
ADVANTAGEOUS EFFECTS OF INVENTION
The dispersion maintaining agent of the present invention can sufficiently prevent slump loss of a hydraulic composition. When the dispersion-retaining agent of the present invention is used in combination with the above-mentioned water-soluble vinyl copolymer which has been proposed as a dispersant for hydraulic compositions, the effects of both of them act synergistically to impart excellent fluidity to hydraulic compositions over time.
Detailed Description
Examples
Hereinafter, examples and the like are given to explain the structure of the present invention more specifically, but the present invention is not limited to these examples. In the following examples and the like, unless otherwise specified,% represents% by mass and parts represent parts by mass.
Test class 1 (Synthesis of monomer A)
Synthesis of monomer (A-5)
127.7g of hydroxyethyl acrylate, 192.1g of trimellitic anhydride, 0.64g of 4-methoxyphenol and 300mL of pyridine were put in a reaction vessel equipped with a thermometer, a stirrer and an air inlet tube, and after uniformly dissolving them under stirring, the temperature was raised while blowing dry air at a flow rate of 5 mL/min, and the reaction was carried out at 80 ℃ for 8 hours. After the reaction was terminated, pyridine was distilled off by an evaporator to obtain a monoester of hydroxyethyl acrylate and trimellitic acid (A-5).
Synthesis of monomer (A-6)
130.1g of hydroxypropyl acrylate, 110.1g of succinic anhydride and 0.13g of phenothiazine were charged into a reaction vessel equipped with a thermometer, a stirrer and an air inlet tube, and the temperature was raised while blowing dry air at a flow rate of 3 mL/min, and the reaction was carried out at 100 ℃ for 10 hours. After the reaction was terminated, cooling was conducted to obtain a monoester of hydroxypropyl acrylate and succinic acid (A-6).
Test class 2 (Synthesis of vinyl copolymer)
Example 1{ Synthesis of vinyl copolymer (EX-1) }
29.2g of ion-exchanged water and 174.2g of α - (3-methyl-3-butenyl) - ω -hydroxy-poly (n ═ 53) ethylene oxide were put into a reaction vessel equipped with a thermometer, a stirrer, a dropping funnel and a nitrogen introduction tube, and after uniformly dissolving them under stirring, the atmosphere was replaced with nitrogen, and the temperature of the reaction system was adjusted to 65 ℃ by a warm water bath. Then, 10.8g of 3.5% hydrogen peroxide was added dropwise over 3 hours, while an aqueous solution in which 15.2g of 2-acryloyloxyethylsuccinic acid and 28.3g of hydroxyethyl acrylate were suspended was added dropwise over 3 hours to 174.2g of ion-exchanged water, and an aqueous solution in which 1.0g of L-ascorbic acid and 0.8g of mercaptoethanol were dissolved was added dropwise over 4 hours to 7.3g of ion-exchanged water. Thereafter, the reaction mixture was maintained at 65 ℃ for 2 hours to terminate the polymerization reaction. After completion of the polymerization reaction, a 30% aqueous solution of sodium hydroxide was added to adjust the reaction mixture to a pH of 6 and the concentration of the reaction mixture was adjusted to 40% by ion-exchanged water to obtain an aqueous solution of the reaction product. This reaction product was used as a vinyl copolymer (EX-1).
Example 2 Synthesis of vinyl copolymer (EX-2)
Ion-exchanged water 206.5g, α -methacryloyl- ω -methoxy-poly (n ═ 23) ethylene oxide 151.7g, 2-methacryloyloxyethylsuccinic acid 23.3g, hydroxyethyl acrylate 19.4g, and 3-mercaptopropionic acid 2.3g were put in the same reaction vessel as in example 1, and the atmosphere was replaced with nitrogen under stirring, and the temperature of the reaction system was adjusted to 70 ℃ by a warm water bath. 28.0g of an aqueous solution of 3.0% sodium persulfate was added to initiate the reaction. After 3 hours from the start of the reaction, 6.8g of a 3.0% aqueous solution of sodium persulfate was added and the mixture was held at 70 ℃ for 3 hours to terminate the polymerization reaction. Then, 30% aqueous sodium hydroxide solution was added to adjust the reaction mixture to pH6, and the concentration was adjusted to 40% by ion-exchanged water, thereby obtaining an aqueous solution of the reaction product. This reaction product was used as a vinyl copolymer (EX-2).
Example 3 Synthesis of vinyl copolymer (EX-3)
27.9g of ion-exchanged water and 173.0g of α - (3-methyl-3-butenyl) - ω -hydroxy-poly (n ═ 53) ethylene oxide were put into the same reaction vessel as in example 1, and uniformly dissolved with stirring, and then the atmosphere was replaced with nitrogen, and the temperature of the reaction system was adjusted to 65 ℃ by a warm water bath. Then, 10.8g of 3.5% hydrogen peroxide was added dropwise over 3 hours, and simultaneously, 43.2g of an aqueous solution in which 2-acryloyloxyethylsuccinic acid was suspended was added dropwise over 3 hours to 173.0g of ion-exchanged water, and an aqueous solution in which 0.9g of L-ascorbic acid and 0.7g of 3-mercaptopropionic acid were dissolved was added dropwise over 4 hours to 6.1g of ion-exchanged water. Thereafter, the reaction mixture was maintained at 65 ℃ for 2 hours to terminate the polymerization reaction. After completion of the polymerization reaction, a 30% aqueous solution of sodium hydroxide was added to adjust the reaction mixture to a pH of 6 and the concentration of the reaction mixture was adjusted to 40% by ion-exchanged water to obtain an aqueous solution of the reaction product. This reaction product was used as a vinyl copolymer (EX-3).
Example 4{ Synthesis of vinyl copolymer (EX-4) }
Ion-exchanged water 36.4g and α - (3-methyl-3-butenyl) - ω -hydroxy-poly (n ═ 53) ethylene oxide 173.5g were put into the same reaction vessel as in example 1, and uniformly dissolved with stirring, and then the atmosphere was replaced with nitrogen, and the temperature of the reaction system was adjusted to 65 ℃ by a warm water bath. Then, 9.8g of 4.0% hydrogen peroxide was added dropwise over 3 hours, and an aqueous solution in which 15.2g of 2-acryloyloxyethylsuccinic acid, 26.0g of hydroxyethyl acrylate, and 2.2g of acrylic acid were dissolved was added dropwise over 3 hours to 164.8g of ion-exchanged water, and an aqueous solution in which 0.9g of L-ascorbic acid and 1.1g of 3-mercaptopropionic acid were dissolved was added dropwise over 4 hours to 7.8g of ion-exchanged water. Thereafter, the reaction mixture was maintained at 65 ℃ for 2 hours to terminate the polymerization reaction. After completion of the polymerization reaction, a 30% aqueous solution of sodium hydroxide was added to adjust the reaction mixture to a pH of 6 and the concentration of the reaction mixture was adjusted to 40% by ion-exchanged water to obtain an aqueous solution of the reaction product. This reaction product was used as a vinyl copolymer (EX-4).
Examples 5 to 9{ Synthesis of vinyl copolymers (EX-5) to (EX-9) }
Vinyl copolymers (EX-5) to (EX-9) were synthesized in the same manner as in examples 1 to 4, except that the kinds, amounts and the like of the monomers used were changed as shown in Table 1.
Comparative example 1{ Synthesis of vinyl copolymer (CE-1) }
242.8g of ion-exchanged water, 370.0g of α - (3-methyl-3-butenyl) - ω -hydroxy-poly (n ═ 53) ethylene oxide, and 0.7g of acrylic acid were put into the same reaction vessel as in example 1, and uniformly dissolved with stirring, and then the atmosphere was replaced with nitrogen, and the temperature of the reaction system was adjusted to 60 ℃ by a warm water bath. Then, 48.8g of a 4.3% aqueous solution of sodium persulfate was added dropwise over 3.5 hours, and at the same time, an aqueous solution in which 18.7g of acrylic acid was dissolved was added dropwise to 21.6g of ion-exchanged water over 3 hours, and an aqueous solution in which 0.7g of mercaptoethanol was dissolved was added dropwise to 46.7g of ion-exchanged water over 3.5 hours. Thereafter, the reaction mixture was maintained at 60 ℃ for 2 hours to terminate the polymerization reaction. After completion of the polymerization reaction, a 30% aqueous solution of sodium hydroxide was added to adjust the reaction mixture to a pH of 6 and the concentration of the reaction mixture was adjusted to 40% by ion-exchanged water to obtain an aqueous solution of the reaction product. This reaction product was used as a vinyl copolymer (CE-1).
Comparative example 2{ adjustment of CE-2 }
The sodium gluconate is adjusted to a concentration of 40% by means of ion-exchange water.
The composition and mass average molecular weight of each of the vinyl copolymers synthesized above are shown in table 1. After removing water from the aqueous solution of each vinyl copolymer, the solution was adjusted to 5% with heavy water, and the polymerization of each monomer was confirmed by NMR measurement at 300 MHz. The mass average molecular weight was measured by GPC and expressed in terms of polyethylene glycol.
[ Table 1]
In the context of table 1, the following,
a-1: 2-Acryloxyethylsuccinic acid
A-2: 2-Methacryloyloxyethyl succinic acid
A-3: 2-Acryloxyethylhexahydrophthalic acid
A-4: 2-acryloyloxyethyl phthalic acid
A-5: monoesters of hydroxyethyl acrylate and trimellitic acid
A-6: monoesters of hydroxypropyl acrylate and succinic acid
M-1: alpha- (3-methyl-3-butenyl) -omega-hydroxy-poly (n ═ 53) ethylene oxide
M-2: alpha-methacryl-omega-methoxy-poly (n ═ 23) ethylene oxide
M-3: alpha-methacryl-omega-methoxy-poly (n ═ 45) ethylene oxide
M-4: alpha-methallyl-omega-hydroxy-poly (n ═ 113) ethylene oxide
M-5: alpha-methacryl-omega-methoxy-poly (n ═ 9) ethylene oxide
M-6: hydroxy ethyl acrylate
M-7: acrylic acid methyl ester
M-8: hydroxy propyl acrylate
C-1: acrylic acid
C-2: methacrylic acid
Test class 3 (evaluation as a dispersant for Hydraulic compositions)
Preparation of the concrete
Ordinary portland cement (manufactured by pacific cement corporation, specific gravity 3.16), fine aggregate (Dajing river system sand, specific gravity 2.58) and coarse aggregate (crushed stone produced by Okazaki Katsuka, specific gravity 2.68) were put into a 55L forced twin-screw mixer in this order, and after dry-mixing for 5 seconds, in order to achieve a target slump of 21. + -. 1.5cm and an air amount of 4.5. + -. 0.5%, a 20% aqueous solution of high-performance AE water reducing agents (trade name CHUPOL HP-11, hereinafter referred to as HP-11, manufactured by bamboo oil and fat Co., Ltd.) and 0.1 to 0.3% of vinyl copolymers (EX-1) to (EX-9) and (CE-1) synthesized in test category 2, which are synthesized with respect to ordinary portland cement, and a 20% aqueous solution of AE-2, and a 0.005% aqueous solution of cement (trade name of bamboo oil and fat Co., manufactured by bamboo oil and fat Co., Ltd.) were put together with mixing and stirring water, An antifoaming agent (trade name AFK-2 manufactured by bamboo oil & fat Co., Ltd.) was added to ordinary portland cement in an amount of 0.001%, and the mixture was mixed and stirred for 90 seconds. The unit amount and the like of the concrete prepared in this way are shown in table 2.
[ Table 2]
Evaluation of
Immediately after the mixing and stirring, slump flow, air amount, and compressive strength and bleeding rate after 24 hours of standing concrete were measured at 30-minute intervals as follows, and the results are summarized in table 3.
Slump flow: the concrete samples immediately after the mixing and stirring and after the standing at 30 minute intervals were measured in accordance with JIS-A1150.
Air amount: the concrete samples immediately after the mixing and stirring and after the standing at 30 minute intervals were measured in accordance with JIS-A1128.
Compressive strength: the sample size was measured in accordance with JIS-A1108 at a diameter of 100mm X a height of 200mm at age of 24 hours.
Bleeding rate: measured according to JIS-A1123.
[ Table 3]
In the context of Table 3, the following examples are,
HP-11 addition ratio (%): mass% relative to ordinary Portland cement in the case of HP-11%
Addition ratio (%) of vinyl copolymer: 20% aqueous liquid of the vinyl copolymer synthesized in test class 2, etc. to the mass% of ordinary portland cement%
From the results of table 3 corresponding to tables 1 and 2, the fluidity of the hydraulic composition can be maintained for a long time without causing delay in hardening by the dispersion retaining agent of the present invention.
Claims (11)
1. A dispersion maintaining agent for hydraulic compositions, characterized by comprising a vinyl copolymer obtained from a monomer A represented by the following chemical formula 1 and a monomer B represented by the following chemical formula 2,
[ chemical formula 1]
[ chemical formula 2]
In chemical formula 1 and chemical formula 2,
R1、R2: a hydrogen atom, a methyl group, or an organic group represented by chemical formula 3;
p: 0 or 1;
x: an organic group represented by the following chemical formula 4;
y: an organic group represented by the following chemical formula 5;
M1: hydrogen atoms, ammonium groups, organic amine groups, alkali metals or 1/2 equivalents of alkaline earth metals;
[ chemical formula 3]
-(CH2)r-COOM2
In the chemical formula 3, the first and second,
r: 0 or 1;
M2: hydrogen atoms, ammonium groups, organic amine groups, alkali metals or 1/2 equivalents of alkaline earth metals;
[ chemical formula 4]
-(AO)m-R3-
In the chemical formula 4, the first and second,
AO: an oxyalkylene group having 2 to 4 carbon atoms;
m: 1 to 10;
R3: alkylene with or without hetero atoms, aromatic cyclic groups or unsaturated hydrocarbon groups;
[ chemical formula 5]
-(CH2)s(CO)tO(AO)n-R4
In the chemical formula 5, the first and second,
s: an integer of 0 to 4;
t: 0 or 1;
AO: an oxyalkylene group having 2 to 4 carbon atoms;
n: an integer of 0 to 300;
R4: a hydrogen atom, an alkyl group having 1 to 22 carbon atoms or an aliphatic acyl group having 1 to 22 carbon atoms, wherein R is 04Is an alkyl group having 1 to 22 carbon atoms or an aliphatic acyl group having 1 to 22 carbon atoms.
2. The dispersion-retaining agent for hydraulic compositions according to claim 1, wherein R in chemical formula 43Is an organic group represented by the following chemical formula 6,
[ chemical formula 6]
In the chemical formula 6, the metal oxide is represented by,
R5: an alkylene group having 1 to 22 carbon atoms, an aromatic ring group or an unsaturated hydrocarbon group, with or without a hetero atom;
u: an integer of 0 to 2;
M3: hydrogen atoms, ammonium groups, organic amine groups, alkali metals or 1/2 equivalents of alkaline earth metals.
3. The dispersion-maintaining agent for hydraulic compositions according to claim 2, wherein R in chemical formula 65Is an alkylene group having 1 to 6 carbon atoms, an aromatic ring group or an unsaturated hydrocarbon group.
4. The dispersion-retaining agent for a hydraulic composition according to any one of claims 1 to 3, wherein the monomer A is a condensate of hydroxyethyl (meth) acrylate and a 2-to 4-membered carboxylic acid anhydride.
5. The dispersion-retaining agent for a hydraulic composition according to any one of claims 1 to 3, wherein the vinyl copolymer has a mass average molecular weight of 8000 to 200000.
6. The dispersion-retaining agent for a hydraulic composition according to any one of claims 1 to 3, wherein the vinyl copolymer has a structural unit derived from the monomer A in a proportion of 1 to 99 mol% and a structural unit derived from the monomer B in a proportion of 1 to 99 mol% in the total of the structural units, and the total proportion is 100 mol%.
7. A dispersion maintaining agent for hydraulic compositions, characterized by comprising a vinyl copolymer obtained from a monomer A represented by the following chemical formula 1, a monomer B represented by the following chemical formula 2, and another monomer C copolymerizable with these monomers,
[ chemical formula 1]
[ chemical formula 2]
In chemical formula 1 and chemical formula 2,
R1、R2: a hydrogen atom, a methyl group, or an organic group represented by chemical formula 3;
p: 0 or 1;
x: an organic group represented by the following chemical formula 4;
y: an organic group represented by the following chemical formula 5;
M1: hydrogen atoms, ammonium groups, organic amine groups, alkali metals or 1/2 equivalents of alkaline earth metals;
[ chemical formula 3]
-(CH2)r-COOM2
In the chemical formula 3, the first and second,
r: 0 or 1;
M2: hydrogen atoms, ammonium groups, organic amine groups, alkali metals or 1/2 equivalents of alkaline earth metals;
[ chemical formula 4]
-(AO)m-R3-
In the chemical formula 4, the first and second,
AO: an oxyalkylene group having 2 to 4 carbon atoms;
m: 1 to 10;
R3: alkylene with or without hetero atoms, aromatic cyclic groups or unsaturated hydrocarbon groups;
[ chemical formula 5]
-(CH2)s(CO)tO(AO)n-R4
In the chemical formula 5, the first and second,
s: an integer of 0 to 4;
t: 0 or 1;
AO: an oxyalkylene group having 2 to 4 carbon atoms;
n: an integer of 0 to 300;
R4: a hydrogen atom, an alkyl group having 1 to 22 carbon atoms or an aliphatic acyl group having 1 to 22 carbon atoms, wherein R is 04Is an alkyl group having 1 to 22 carbon atoms or an aliphatic acyl group having 1 to 22 carbon atoms.
8. The dispersion-maintaining agent for hydraulic compositions according to claim 7, wherein R in chemical formula 43Is an organic group represented by the following chemical formula 6,
[ chemical formula 6]
In the chemical formula 6, the metal oxide is represented by,
R5: an alkylene group having 1 to 22 carbon atoms, an aromatic ring group or an unsaturated hydrocarbon group, with or without a hetero atom;
u: an integer of 0 to 2;
M3: hydrogen atoms, ammonium groups, organic amine groups, alkali metals or 1/2 equivalents of alkaline earth metals.
9. The dispersion-maintaining agent for hydraulic compositions according to claim 8, wherein R in chemical formula 65Is an alkylene group having 1 to 6 carbon atoms, an aromatic ring group or an unsaturated hydrocarbon group.
10. The dispersion-retaining agent for a hydraulic composition according to any one of claims 7 to 9, wherein the monomer A is a condensate of hydroxyethyl (meth) acrylate and a 2-to 4-membered carboxylic acid anhydride.
11. The dispersion-retaining agent for a hydraulic composition according to any one of claims 7 to 9, wherein the vinyl copolymer has a mass average molecular weight of 8000 to 200000.
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| JP4502344B2 (en) * | 2000-06-15 | 2010-07-14 | 太平洋セメント株式会社 | Gypsum dispersant |
| JP4141119B2 (en) | 2001-07-24 | 2008-08-27 | 竹本油脂株式会社 | Fluidity reduction inhibitor for concrete and method for preventing fluidity reduction of concrete |
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| JP4707197B2 (en) * | 2008-10-23 | 2011-06-22 | 竹本油脂株式会社 | Method for preparing low shrinkage AE concrete for civil engineering and low shrinkage AE concrete for civil engineering |
| JP6739781B2 (en) * | 2016-04-15 | 2020-08-12 | 竹本油脂株式会社 | Dispersion holding agent for hydraulic composition, method for using dispersion holding agent for hydraulic composition, and method for preparing hydraulic composition |
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2017
- 2017-09-12 WO PCT/JP2017/032877 patent/WO2019053782A1/en active Application Filing
- 2017-09-12 CN CN201780094648.1A patent/CN111051265B/en active Active
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| US5135577A (en) * | 1990-11-05 | 1992-08-04 | Halliburton Company | Composition and method for inhibiting thermal thinning of cement |
| CN1473863A (en) * | 2002-08-06 | 2004-02-11 | 上海合达聚合物科技有限公司 | Process for preparing water dispersion of crosslinking vinyl resin/polyurethane hybrid resin |
| EP1491516A3 (en) * | 2003-06-24 | 2008-02-20 | Hewlett-Packard Development Company, L.P. | Calcium aluminate cement compositions for solid freeform fabrication |
| CN1954001A (en) * | 2004-03-18 | 2007-04-25 | 伯斯蒂克公司 | Process for preparing an aqueous dispersion of a quaternary ammonium salt containing vinyl copolymer |
| CN104204008A (en) * | 2012-02-03 | 2014-12-10 | 帝斯曼知识产权资产管理有限公司 | Polymer, process and composition |
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| PH12020500481A1 (en) | 2021-03-01 |
| WO2019053782A1 (en) | 2019-03-21 |
| KR102192163B1 (en) | 2020-12-16 |
| KR20200029605A (en) | 2020-03-18 |
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