CN116063021A - Additive for hydraulic composition and hydraulic composition - Google Patents
Additive for hydraulic composition and hydraulic composition Download PDFInfo
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- CN116063021A CN116063021A CN202210961549.1A CN202210961549A CN116063021A CN 116063021 A CN116063021 A CN 116063021A CN 202210961549 A CN202210961549 A CN 202210961549A CN 116063021 A CN116063021 A CN 116063021A
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- 239000000203 mixture Substances 0.000 title claims abstract description 115
- 239000000654 additive Substances 0.000 title description 13
- 230000000996 additive effect Effects 0.000 title description 8
- 150000001875 compounds Chemical class 0.000 claims abstract description 49
- 229920006163 vinyl copolymer Polymers 0.000 claims abstract description 37
- 239000000470 constituent Substances 0.000 claims abstract description 30
- 125000004432 carbon atom Chemical group C* 0.000 claims description 38
- 125000005702 oxyalkylene group Chemical group 0.000 claims description 34
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 33
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 16
- 125000002947 alkylene group Chemical group 0.000 claims description 15
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 11
- 229910052751 metal Inorganic materials 0.000 claims description 11
- 239000002184 metal Substances 0.000 claims description 11
- -1 tetracarboxylic anhydride Chemical class 0.000 claims description 11
- 150000001412 amines Chemical class 0.000 claims description 10
- 125000004429 atom Chemical group 0.000 claims description 10
- 125000000217 alkyl group Chemical group 0.000 claims description 9
- 125000000954 2-hydroxyethyl group Chemical group [H]C([*])([H])C([H])([H])O[H] 0.000 claims description 8
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 8
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 8
- UZDMJPAQQFSMMV-UHFFFAOYSA-N 4-oxo-4-(2-prop-2-enoyloxyethoxy)butanoic acid Chemical compound OC(=O)CCC(=O)OCCOC(=O)C=C UZDMJPAQQFSMMV-UHFFFAOYSA-N 0.000 claims description 6
- 125000003118 aryl group Chemical group 0.000 claims description 5
- 125000004122 cyclic group Chemical group 0.000 claims description 5
- RKYJPYDJNQXILT-UHFFFAOYSA-N 2-(2-prop-2-enoyloxyethoxycarbonyl)benzoic acid Chemical compound OC(=O)C1=CC=CC=C1C(=O)OCCOC(=O)C=C RKYJPYDJNQXILT-UHFFFAOYSA-N 0.000 claims description 3
- UECGJSXCVLTIMQ-UHFFFAOYSA-N 2-(2-prop-2-enoyloxyethoxycarbonyl)cyclohexane-1-carboxylic acid Chemical compound OC(=O)C1CCCCC1C(=O)OCCOC(=O)C=C UECGJSXCVLTIMQ-UHFFFAOYSA-N 0.000 claims description 3
- 230000014759 maintenance of location Effects 0.000 abstract description 21
- 238000002156 mixing Methods 0.000 description 24
- 238000006243 chemical reaction Methods 0.000 description 18
- 239000011230 binding agent Substances 0.000 description 17
- 239000008399 tap water Substances 0.000 description 17
- 235000020679 tap water Nutrition 0.000 description 17
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 15
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 13
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 12
- 238000005227 gel permeation chromatography Methods 0.000 description 12
- 238000004519 manufacturing process Methods 0.000 description 11
- 125000006032 3-methyl-3-butenyl group Chemical group 0.000 description 10
- 239000003795 chemical substances by application Substances 0.000 description 10
- 239000011541 reaction mixture Substances 0.000 description 10
- 239000007864 aqueous solution Substances 0.000 description 9
- 239000004568 cement Substances 0.000 description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 9
- 230000000694 effects Effects 0.000 description 8
- 238000011156 evaluation Methods 0.000 description 8
- 229910052757 nitrogen Inorganic materials 0.000 description 8
- 239000011398 Portland cement Substances 0.000 description 7
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 7
- 230000015572 biosynthetic process Effects 0.000 description 7
- 238000003786 synthesis reaction Methods 0.000 description 7
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 6
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 6
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 6
- DKIDEFUBRARXTE-UHFFFAOYSA-N 3-mercaptopropanoic acid Chemical compound OC(=O)CCS DKIDEFUBRARXTE-UHFFFAOYSA-N 0.000 description 5
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 5
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical group CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 5
- 239000004576 sand Substances 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- 239000012298 atmosphere Substances 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 239000000178 monomer Substances 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- 238000006116 polymerization reaction Methods 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- 239000000376 reactant Substances 0.000 description 4
- 150000003839 salts Chemical class 0.000 description 4
- 238000001179 sorption measurement Methods 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 239000004575 stone Substances 0.000 description 4
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 description 3
- 239000002211 L-ascorbic acid Substances 0.000 description 3
- 235000000069 L-ascorbic acid Nutrition 0.000 description 3
- 239000002518 antifoaming agent Substances 0.000 description 3
- 229960005070 ascorbic acid Drugs 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 239000006185 dispersion Substances 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 3
- 125000006353 oxyethylene group Chemical group 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 239000002893 slag Substances 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- CWERGRDVMFNCDR-UHFFFAOYSA-N thioglycolic acid Chemical compound OC(=O)CS CWERGRDVMFNCDR-UHFFFAOYSA-N 0.000 description 3
- 235000017166 Bambusa arundinacea Nutrition 0.000 description 2
- 235000017491 Bambusa tulda Nutrition 0.000 description 2
- 241001330002 Bambuseae Species 0.000 description 2
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 2
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 2
- IOVCWXUNBOPUCH-UHFFFAOYSA-M Nitrite anion Chemical compound [O-]N=O IOVCWXUNBOPUCH-UHFFFAOYSA-M 0.000 description 2
- 235000015334 Phyllostachys viridis Nutrition 0.000 description 2
- 150000005215 alkyl ethers Chemical class 0.000 description 2
- 239000003945 anionic surfactant Substances 0.000 description 2
- 239000011425 bamboo Substances 0.000 description 2
- 150000001720 carbohydrates Chemical class 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical class OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 2
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 2
- 125000002843 carboxylic acid group Chemical group 0.000 description 2
- 229920003086 cellulose ether Polymers 0.000 description 2
- 239000003638 chemical reducing agent Substances 0.000 description 2
- YDEXUEFDPVHGHE-GGMCWBHBSA-L disodium;(2r)-3-(2-hydroxy-3-methoxyphenyl)-2-[2-methoxy-4-(3-sulfonatopropyl)phenoxy]propane-1-sulfonate Chemical compound [Na+].[Na+].COC1=CC=CC(C[C@H](CS([O-])(=O)=O)OC=2C(=CC(CCCS([O-])(=O)=O)=CC=2)OC)=C1O YDEXUEFDPVHGHE-GGMCWBHBSA-L 0.000 description 2
- 239000003480 eluent Substances 0.000 description 2
- 125000004185 ester group Chemical group 0.000 description 2
- 239000010881 fly ash Substances 0.000 description 2
- 239000003112 inhibitor Substances 0.000 description 2
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 2
- 239000003755 preservative agent Substances 0.000 description 2
- 230000002335 preservative effect Effects 0.000 description 2
- 229910021487 silica fume Inorganic materials 0.000 description 2
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 description 2
- ARCGXLSVLAOJQL-UHFFFAOYSA-N trimellitic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C(C(O)=O)=C1 ARCGXLSVLAOJQL-UHFFFAOYSA-N 0.000 description 2
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 235000019738 Limestone Nutrition 0.000 description 1
- 229920000877 Melamine resin Polymers 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- ACIAHEMYLLBZOI-ZZXKWVIFSA-N Unsaturated alcohol Chemical compound CC\C(CO)=C/C ACIAHEMYLLBZOI-ZZXKWVIFSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 238000007259 addition reaction Methods 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 150000004703 alkoxides Chemical class 0.000 description 1
- 239000011400 blast furnace cement Substances 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- JPZYWLWSLROXQG-UHFFFAOYSA-N ethyl 2-prop-2-enoylperoxycarbonylbenzoate Chemical compound CCOC(=O)C1=CC=CC=C1C(=O)OOC(=O)C=C JPZYWLWSLROXQG-UHFFFAOYSA-N 0.000 description 1
- YTNAFAADLMGGPI-UHFFFAOYSA-N ethyl 2-prop-2-enoylperoxycarbonylcyclohexane-1-carboxylate Chemical compound CCOC(=O)C1CCCCC1C(=O)OOC(=O)C=C YTNAFAADLMGGPI-UHFFFAOYSA-N 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 239000005457 ice water Substances 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- SURQXAFEQWPFPV-UHFFFAOYSA-L iron(2+) sulfate heptahydrate Chemical compound O.O.O.O.O.O.O.[Fe+2].[O-]S([O-])(=O)=O SURQXAFEQWPFPV-UHFFFAOYSA-L 0.000 description 1
- 239000009628 lidan Substances 0.000 description 1
- 239000006028 limestone Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 description 1
- 229910000000 metal hydroxide Inorganic materials 0.000 description 1
- 150000004692 metal hydroxides Chemical class 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000004570 mortar (masonry) Substances 0.000 description 1
- LNOPIUAQISRISI-UHFFFAOYSA-N n'-hydroxy-2-propan-2-ylsulfonylethanimidamide Chemical compound CC(C)S(=O)(=O)CC(N)=NO LNOPIUAQISRISI-UHFFFAOYSA-N 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 235000010344 sodium nitrate Nutrition 0.000 description 1
- 239000004317 sodium nitrate Substances 0.000 description 1
- UCWBKJOCRGQBNW-UHFFFAOYSA-M sodium;hydroxymethanesulfinate;dihydrate Chemical compound O.O.[Na+].OCS([O-])=O UCWBKJOCRGQBNW-UHFFFAOYSA-M 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000001384 succinic acid Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
Classifications
-
- 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
- C04B24/28—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- C04B24/32—Polyethers, e.g. alkylphenol polyglycolether
-
- 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
- C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
- C08F283/06—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polyethers, polyoxymethylenes or polyacetals
- C08F283/065—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polyethers, polyoxymethylenes or polyacetals on to unsaturated polyethers, polyoxymethylenes or polyacetals
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
- Y02W30/50—Reuse, recycling or recovery technologies
- Y02W30/91—Use of waste materials as fillers for mortars or concrete
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Ceramic Engineering (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Structural Engineering (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Curing Cements, Concrete, And Artificial Stone (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
The present invention relates to an admixture for hydraulic compositions and a hydraulic composition. The present invention provides an admixture for a hydraulic composition, which can exhibit both excellent initial dispersibility and excellent flow retention in a hydraulic composition by using the admixture in the hydraulic composition. An admixture for hydraulic compositions, which comprises a water-soluble vinyl copolymer having a structure unit 1 formed from a compound represented by the general formula (1), a structure unit 2 formed from a compound represented by the general formula (2), and a structure unit 3 formed from a compound represented by the general formula (3) in the molecule, wherein the structure unit 1 is contained in a proportion of 65 to 95 mass% and the structure unit 2 is contained in a proportion of 2 to 30 mass% and the structure unit 3 is contained in a proportion of 0.1 to 25 mass% when the total of the constituent proportions of the structure unit 1, the structure unit 2, and the structure unit 3 is taken as 100 mass%.
Description
Technical Field
The present invention relates to an admixture for hydraulic compositions and a hydraulic composition. More specifically, the present invention relates to an admixture for hydraulic compositions and a hydraulic composition having excellent initial dispersibility and flow retention.
Background
Conventionally, in order to improve the fluidity and flow retention of hydraulic compositions such as mortar and concrete, various additives for hydraulic compositions such as naphthalene-based, melamine-based, sulfamic acid-based, and polycarboxylic acid-based have been used.
In recent years, there has been proposed a method for further improving the flow retention of such an admixture for hydraulic compositions, for example, by using a dispersion (retention) agent for hydraulic compositions containing a polymer having a predetermined structure in combination (for example, refer to patent documents 1 to 3).
Prior art literature
Patent literature
Patent document 1: japanese patent application laid-open No. 2010-1199
Patent document 2: japanese patent application laid-open No. 2010-120826
Patent document 3: japanese patent laid-open No. 2014-218619
Disclosure of Invention
However, the dispersing (retaining) agents for hydraulic compositions (admixtures for hydraulic compositions) described in patent documents 1 to 3 have insufficient initial dispersibility when used alone, and there is room for further improvement. In order to improve the versatility, it is required to develop an additive for hydraulic compositions which can exhibit both excellent initial dispersibility and excellent flow retention with one dose.
In view of the above-described circumstances, an object of the present invention is to provide an admixture for a hydraulic composition, which can exhibit both excellent initial dispersibility and excellent flow retention by a single dose, even if it is not blended with a dispersion retention agent for a hydraulic composition, by using the admixture for a hydraulic composition.
The present inventors have made intensive studies to solve the above problems, and as a result, have found that the above problems can be solved by containing a water-soluble vinyl copolymer containing structural units 1 to 3 in a predetermined ratio. According to the present invention, the following admixture for hydraulic compositions and hydraulic compositions are provided.
[1] An admixture for hydraulic compositions, which comprises a water-soluble vinyl copolymer having in the molecule a structural unit 1 formed of a compound represented by the following general formula (1), a structural unit 2 formed of a compound represented by the following general formula (2), and a structural unit 3 formed of a compound represented by the following general formula (3),
when the total of the constituent ratios of the constituent units 1, 2 and 3 is 100% by mass, the constituent unit 1 is contained in a proportion of 65 to 95% by mass, the constituent unit 2 is contained in a proportion of 2 to 30% by mass, and the constituent unit 3 is contained in a proportion of 0.1 to 25% by mass.
(in the general formula (1), R 1 、R 2 、R 3 Each independently is a hydrogen atom or a methyl group. R is R 4 O is an oxyalkylene group having 2 to 4 carbon atoms (wherein, when there are a plurality of the oxyalkylene groups, 1 or 2 or more of the oxyalkylene groups may be used singly). m is an integer of 0 to 2. n is R 4 The average molar number of addition of O is 1 to 300. )
(in the general formula (2), R 5 Is a hydrogen atom or a methyl group. M is M 1 Is a hydrogen atom, a metal atom, ammonium or an organic amine. )
(in the general formula (3), R 6 Is a hydrogen atom or a methyl group. R is R 7 O is an oxyalkylene group having 2 to 4 carbon atoms (wherein, when there are a plurality of the oxyalkylene groups, 1 or 2 or more of the oxyalkylene groups may be used singly). R is R 8 Is a chain alkylene group having 1 to 22 carbon atoms, a cyclic alkylene group having 3 to 10 carbon atoms, or an aryl group having 6 to 22 carbon atoms. p is R 7 The average molar number of addition of O is 1 to 5. q is an integer of 0 to 2. M is M 2 、M 3 Each independently is a hydrogen atom, a metal atom, ammonium or an organic amine. )
[2] The admixture for hydraulic compositions according to the above [1], wherein the compound represented by the above general formula (3) forming the above structural unit 3 contains a condensate of 2-hydroxyethyl (meth) acrylate and a di-to tetracarboxylic anhydride.
[3] The admixture for hydraulic compositions according to the above [1] or [2], wherein the compound represented by the above general formula (3) forming the above structural unit 3 contains at least one member selected from the group consisting of 2- (meth) acryloyloxyethyl succinate, 2- (meth) acryloyloxyethyl hexahydrophthalate and 2- (meth) acryloyloxyethyl phthalate.
[4] The admixture for hydraulic compositions according to any one of the above [1] to [3], wherein the water-soluble vinyl copolymer further comprises a structural unit 4 formed of a compound represented by the following general formula (4) in a molecule,
when the total of the constituent ratios of the constituent unit 1, the constituent unit 2, the constituent unit 3, and the constituent unit 4 is 100 mass%, the constituent unit 1 is contained in a proportion of 65 to 95 mass%, the constituent unit 2 is contained in a proportion of 2 to 30 mass%, the constituent unit 3 is contained in a proportion of 0.1 to 10 mass%, and the constituent unit 4 is contained in a proportion of 0.1 to 15 mass%.
(in the general formula (4), R 9 Is a hydrogen atom or a methyl group. R is R 10 O is an oxyalkylene group having 2 to 4 carbon atoms (wherein, when there are a plurality of the oxyalkylene groups, 1 or 2 or more of the oxyalkylene groups may be used singly). R is R 10 The average addition mole number of O is 0 to 10. R is R 11 Is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms. Where r=0, R 11 Is an alkyl group having 1 to 5 carbon atoms. )
[5] The admixture for hydraulic compositions according to the above [4], wherein the compound represented by the general formula (4) forming the above-mentioned structural unit 4 contains 2-hydroxyethyl (meth) acrylate.
[6] The admixture for hydraulic compositions according to any one of the above [1] to [5], wherein the water-soluble vinyl copolymer has a mass average molecular weight of 5000 to 100000.
[7] A hydraulic composition comprising the admixture according to any one of the above [1] to [6 ].
The admixture for hydraulic compositions of the present invention exhibits the following effects: when this is used in a hydraulic composition, it is possible to exert both excellent initial dispersibility and excellent flow retention in the hydraulic composition with only one dose.
The hydraulic composition of the present invention exhibits the following effects: the admixture for hydraulic compositions of the present invention provides both excellent initial dispersibility and excellent flow retention.
Detailed Description
Hereinafter, embodiments of the present invention will be described. However, the present invention is not limited to the following embodiments. Accordingly, it is to be understood that appropriate modifications, improvements, and the like may be made to the following embodiments based on conventional knowledge of those skilled in the art, within the scope of the gist of the present invention. In the following examples and the like, unless otherwise specified,% represents% by mass, and parts represent parts by mass.
(1) Additive for hydraulic compositions:
the admixture for hydraulic compositions of the present invention comprises a water-soluble vinyl copolymer having a molecule comprising a structural unit 1 formed from a compound represented by the following general formula (1), a structural unit 2 formed from a compound represented by the following general formula (2), and a structural unit 3 formed from a compound represented by the following general formula (3). In the water-soluble vinyl copolymer, when the total of the constituent ratios of the constituent units 1, 2 and 3 is 100% by mass, the constituent unit 1 is contained in a proportion of 65 to 95% by mass, the constituent unit 2 is contained in a proportion of 2 to 30% by mass, and the constituent unit 3 is contained in a proportion of 0.1 to 25% by mass.
The admixture for hydraulic compositions contains a water-soluble vinyl copolymer having the above-mentioned predetermined structural units 1 to 3 in a predetermined proportion, and thus can exhibit excellent flow retention in hydraulic compositions with only one dose. Further, by adopting the above-described configuration, the initial dispersibility can be improved, and excellent initial dispersibility can be exhibited.
(in the general formula (1), R 1 、R 2 、R 3 Each independently is a hydrogen atom or a methyl group. R is R 4 O is an oxyalkylene group having 2 to 4 carbon atoms (wherein, when there are a plurality of the oxyalkylene groups, 1 or 2 or more of the oxyalkylene groups may be used singly). m is an integer of 0 to 2. n is R 4 The average molar number of addition of O is 1 to 300. )
(in the general formula (2), R 5 Is a hydrogen atom or a methyl group. M is M 1 Is a hydrogen atom, a metal atom, ammonium or an organic amine. )
(in the general formula (3), R 6 Is a hydrogen atom or a methyl group. R is R 7 O is an oxyalkylene group having 2 to 4 carbon atoms (wherein, when there are a plurality of the oxyalkylene groups, 1 or 2 or more of the oxyalkylene groups may be used singly). R is R 8 Is a chain alkylene group having 1 to 22 carbon atoms, a cyclic alkylene group having 3 to 10 carbon atoms, or an aryl group having 6 to 22 carbon atoms. p is R 7 The average molar number of addition of O is 1 to 5. q is an integer of 0 to 2. M is M 2 、M 3 Each independently is a hydrogen atom, a metal atom, ammonium or an organic amine. )
(1-1) Water-soluble vinyl copolymer:
the water-soluble vinyl copolymer comprises: 65 to 95 mass% of the structural unit 1, 2 to 30 mass% of the structural unit 2, and 0.1 to 25 mass% of the structural unit 3 (wherein the total of the constituent ratios of the structural unit 1, the structural unit 2, and the structural unit 3 is 100 mass%).
By having this water-soluble vinyl copolymer, the structural unit 1 contributes to improving the fluidity of the hydraulic composition by utilizing the dispersion effect of the hydraulic binder (cement or the like) mainly due to the steric hindrance of the (poly) alkylene oxide site, and the structural unit 2 having a carboxylic acid group and the structural unit 3 having a plurality of ester groups adsorb to the binder with time difference, whereby excellent initial dispersibility and flow retention can be obtained.
(1-1 a) structural unit 1:
the structural unit 1 is formed of a compound represented by the above general formula (1). Specifically, the structural unit 1 is one structural unit (structural unit derived from a compound represented by the general formula (1)) constituting a polymer obtained by using a monomer which is a compound represented by the general formula (1) as one of materials. It should be noted that the structural unit 1 may contain 1 or more.
R 1 、R 2 、R 3 Each independently represents a hydrogen atom or a methyl group, and may be the same or different.
R 4 O is an oxyalkylene group having 2 to 4 carbon atoms (wherein the number of the oxyalkylene groups may be 1 or 2 or more, if any), and examples of the oxyalkylene group having 2 to 4 carbon atoms include an oxyethylene group, an oxypropylene group, and a oxybutylene group.
m is an integer of 0 to 2.
n is R 4 The average molar number of addition of O is 1 to 300, preferably 1 to 250, more preferably 1 to 150.
In the present specification, the term "average addition mole number" as calculated from the ratio of the respective raw materials charged at the time of production means the mole number of alkylene oxide per 1 mole of the starting material (alcohol).
Specific examples of the compound represented by the general formula (1) include α - (3-methyl-3-butenyl) - ω -hydroxy- (poly) ethylene oxide, α - (3-methyl-3-butenyl) - ω -hydroxy- (poly) ethylene oxide (poly) propylene oxide, α -methallyl- ω -hydroxy- (poly) ethylene oxide (poly) propylene oxide, α -vinyl- ω -hydroxy-butene (poly) oxide, and the like. The number of the compounds may be 1 alone or 2 or more. Of these, α - (3-methyl-3-butenyl) - ω -hydroxy- (poly) ethylene oxide and α -methallyl- ω -hydroxy- (poly) ethylene oxide are preferable, and α - (3-methyl-3-butenyl) - ω -hydroxy- (poly) ethylene oxide is more preferable.
The compound represented by the general formula (1) can be synthesized, for example, as follows. That is, the compound represented by the general formula (1) can be synthesized by performing an alkylene oxide addition reaction on a specific unsaturated alcohol in the presence of a catalyst such as a metal hydroxide or a metal alkoxide.
(1-1 b) structural unit 2:
the structural unit 2 is formed of a compound represented by the above general formula (2). Specifically, the structural unit 2 is one structural unit (structural unit derived from the compound represented by the general formula (2)) constituting a polymer obtained by using a monomer which is the compound represented by the general formula (2) as one of materials. It should be noted that the structural unit 2 may contain 1 or more.
By having the structural unit 2, the water-soluble vinyl copolymer is adsorbed to the binder (cement or the like). The structural unit 2 has a higher effect of accelerating the adsorption of the copolymer to the binder than the structural unit 3, and causes a time difference in the adsorption to the binder. That is, by having the structural units 2 and 3, the adsorption performance to the adhesive can be continued.
R 5 Is a hydrogen atom or methyl group, preferably a hydrogen atom.
M 1 Is a hydrogen atom, a metal atom, ammonium or an organic amine. Among these, hydrogen atoms and metal atoms are preferable. In the present specification, the term "organic amine" refers to a compound in a state of forming a carboxylic acid and a salt.
Specific examples of the compound represented by the general formula (2) include (meth) acrylic acid and salts thereof. The number of the compounds may be 1 alone or 2 or more. With such a constitution, the hydraulic composition can exhibit more excellent initial dispersibility.
(1-1 c) structural unit 3:
the structural unit 3 is formed of a compound represented by the above general formula (3). Specifically, the structural unit 3 is one structural unit (structural unit derived from the compound represented by the general formula (3)) constituting a polymer obtained by using a monomer which is the compound represented by the general formula (3) as one of materials. It should be noted that the structural unit 3 may contain 1 or more.
By having the structural unit 3, the plurality of ester groups of the structural unit 3 are hydrolyzed by the alkali in the hydraulic composition, and carboxylic acid groups as adsorption points of the binder (cement or the like) gradually appear, whereby the water-soluble vinyl copolymer can be adsorbed to the binder (cement or the like) with a time difference. That is, the hydraulic composition has a small slump change amount and good flow retention.
R 6 Is a hydrogen atom or methyl group, preferably a hydrogen atom.
R 7 O is an oxyalkylene group having 2 to 4 carbon atoms (wherein the number of the oxyalkylene groups may be 1 or 2 or more, if any), and examples of the oxyalkylene group having 2 to 4 carbon atoms include an oxyethylene group, an oxypropylene group, and a oxybutylene group.
R 8 Is a chain alkylene group having 1 to 22 carbon atoms, a cyclic alkylene group having 3 to 10 carbon atoms or an aryl group having 6 to 22 carbon atoms, and among these, a chain having 1 to 5 carbon atoms is preferableAn alkylene group, a cyclic alkylene group having 4 to 8 carbon atoms, or an aryl group having 6 carbon atoms.
p is R 7 The average molar number of addition of O is 1 to 5, preferably 1 or 2.
q is an integer of 0 to 2.
M 2 、M 3 Each independently is a hydrogen atom, a metal atom, ammonium or an organic amine. Among these, hydrogen atoms and metal atoms are preferable. In the present specification, the "organic amine" is a compound that forms a state of a carboxylic acid and a salt.
Specific examples of the compound represented by the general formula (3) include a condensate of 2-hydroxyethyl (meth) acrylate and a di-to tetracarboxylic anhydride. The number of the compounds may be 1 alone or 2 or more.
The compound represented by the above general formula (3) forming the structural unit 3 preferably contains a condensate of 2-hydroxyethyl (meth) acrylate and a di-to tetracarboxylic anhydride, more specifically, preferably contains at least one selected from the group consisting of 2- (meth) acryloyloxyethyl succinate, 2- (meth) acryloyloxyethyl hexahydrophthalate and 2- (meth) acryloyloxyethyl phthalate. With such a configuration, even if the dispersion-maintaining agent for hydraulic compositions is not blended, the hydraulic compositions can exhibit more excellent flow-maintaining properties.
(1-1 d) structural unit 4:
the water-soluble vinyl copolymer may further contain in the molecule a structural unit 4 formed from a compound represented by the following general formula (4). Further comprising such a structural unit 4 can exhibit more excellent flow retention in hydraulic compositions.
(in the general formula (4), R 9 Is a hydrogen atom or a methyl group. R is R 10 O is an oxyalkylene group having 2 to 4 carbon atoms (wherein, when there are a plurality of the oxyalkylene groups, 1 or 2 or more of the oxyalkylene groups may be used singly). R is R 10 The average addition mole number of O is 0 to 10. R is R 11 Is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms. Where r=0, R 11 Is an alkyl group having 1 to 5 carbon atoms. )
The structural unit 4 is a hydrolyzable monomer different from the structural unit 3. By having the structural unit 4, the time for the water-soluble vinyl copolymer to adsorb to the binder (cement or the like) can be further increased, and the performance of the flow retention performance can be arbitrarily adjusted.
R 9 Is a hydrogen atom or methyl group, preferably a hydrogen atom.
R 10 O is an oxyalkylene group having 2 to 4 carbon atoms (wherein the number of the oxyalkylene groups may be 1 or 2 or more, if any), and examples of the oxyalkylene group having 2 to 4 carbon atoms include an oxyethylene group, an oxypropylene group, and a oxybutylene group.
R is R 10 The average addition mole number of O is 0 to 10, preferably 0 to 5, more preferably 1 or 2.
R 11 Is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms. Where r=0, R 11 Is an alkyl group having 1 to 5 carbon atoms.
Examples of the compound represented by the general formula (4) forming the structural unit 4 include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, and alkyl (meth) acrylate. The structural unit 4 may be 1 or 2 or more, and preferably contains 2-hydroxyethyl (meth) acrylate. With such a configuration, even if the dispersion-maintaining agent for hydraulic compositions is not blended, the hydraulic compositions can exhibit more excellent flow-maintaining properties.
(1-1 e) composition ratio:
in the water-soluble vinyl copolymer, when the total of the constituent ratios of the constituent units 1, 2 and 3 is 100% by mass, the constituent unit 1 is present in a ratio of 65 to 95% by mass, the constituent unit 2 is present in a ratio of 2 to 30% by mass, and the constituent unit 3 is present in a ratio of 0.1 to 25% by mass. It is preferable that the structural unit 1 is present in an amount of 70 to 95 mass%, the structural unit 2 is present in an amount of 2 to 20 mass%, the structural unit 3 is present in an amount of 0.1 to 20 mass%, the structural unit 1 is present in an amount of 75 to 95 mass%, the structural unit 2 is present in an amount of 3 to 15 mass%, and the structural unit 3 is present in an amount of 0.5 to 15 mass%. By setting the content in this range, both excellent initial dispersibility and excellent flow retention in the hydraulic composition can be exhibited without adding a dispersion-retaining agent for the hydraulic composition. In particular, if the proportion of the structural unit 2 is less than the lower limit value, the initial dispersibility cannot be sufficiently obtained.
When the water-soluble vinyl copolymer further contains the structural unit 4, the total of the constituent proportions of the structural unit 1, the structural unit 2, the structural unit 3 and the structural unit 4 in the water-soluble vinyl copolymer is preferably 65 to 95 mass%, the structural unit 1 is preferably 2 to 30 mass%, the structural unit 3 is preferably 0.1 to 10 mass%, and the structural unit 4 is preferably 0.1 to 15 mass%. It is preferable that the structural unit 1 is contained in an amount of 70 to 95 mass%, the structural unit 2 is contained in an amount of 2 to 20 mass%, the structural unit 3 is contained in an amount of 0.1 to 8 mass%, the structural unit 4 is contained in an amount of 0.5 to 12 mass%, the structural unit 1 is contained in an amount of 75 to 95 mass%, the structural unit 2 is contained in an amount of 3 to 15 mass%, the structural unit 3 is contained in an amount of 0.5 to 5 mass%, and the structural unit 4 is contained in an amount of 1 to 10 mass%. By setting the content to such a range, both of more excellent initial dispersibility and more excellent flow retention can be exhibited in the hydraulic composition.
(1-1 f) mass average molecular weight:
the mass average molecular weight of the water-soluble vinyl copolymer contained in the admixture for hydraulic compositions may be 5000 to 100000, preferably 8000 to 80000, and more preferably 10000 to 80000. By setting the content to such a range, even if the dispersion-maintaining agent for hydraulic compositions is not blended, both of more excellent initial dispersibility and more excellent flow-maintaining property can be exhibited in the hydraulic compositions.
The mass average molecular weight of the water-soluble vinyl copolymer contained in the admixture for hydraulic compositions can be measured by Gel Permeation Chromatography (GPC).
(1-1 g) other ingredients:
the admixture for hydraulic compositions of the present invention may further contain other components in addition to the water-soluble vinyl copolymer. The reaction mixture obtained in the synthesis of the water-soluble vinyl copolymer may be used as an admixture for hydraulic compositions.
Examples of the other components include a coagulation-delaying component composed of a saccharide, a hydroxycarboxylic acid salt, etc., a component having a dispersing action composed of sodium lignin sulfonate, etc., an AE agent composed of an anionic surfactant, etc., an antifoaming agent composed of an alkylene oxide compound, etc., a hardening accelerator composed of an alkanolamine, etc., a shrinkage-reducing agent composed of a polyoxyalkylene alkyl ether, etc., a tackifier composed of a cellulose ether compound, etc., a preservative composed of an isothiazoline compound, etc., a rust inhibitor composed of a nitrite, etc.
(1-1 h) manufacturing method:
the admixture for hydraulic compositions of the present invention can be suitably produced by a conventionally known method such as synthesizing a water-soluble vinyl copolymer so as to contain each of the structural units 1 to 3 (or each of the structural units 1 to 4) in a predetermined content.
(2) Hydraulic composition:
the hydraulic composition of the present invention contains the admixture for a hydraulic composition of the present invention. Such a hydraulic composition can exhibit both excellent initial dispersibility and excellent flow retention properties by using the admixture for a hydraulic composition of the present invention.
The hydraulic composition of the present invention may contain a binder, water, fine aggregate and coarse aggregate, similarly to the conventionally known hydraulic compositions.
The content of the admixture for a hydraulic composition of the present invention in the hydraulic composition of the present invention may be appropriately set without particular limitation, and the content of the admixture for a hydraulic composition of the present invention may be, for example, 0.001 to 3.0 mass% in terms of solid content relative to 100 mass% of the binder.
Examples of the binder include various portland cements such as ordinary portland cement, medium heat portland cement, low heat portland cement, early strength portland cement, and sulfate-resistant portland cement, and various cements such as blast furnace cement, fly ash cement, and silica fume cement.
In addition, the binder may be used in combination with various cements as described above, as various admixtures such as fly ash, fine blast furnace slag powder, fine limestone powder, stone powder, silica fume, and an expansive material.
Examples of the fine aggregate include river sand, mountain sand, liu Sha, sea sand, silica sand, crushed sand, various slag fine aggregates, and the like, and may contain a fine particle component such as clay.
Examples of the coarse aggregate include river gravel, mountain gravel, liu Lidan, crushed stone, various slag coarse aggregates, and lightweight aggregates.
The hydraulic composition of the present invention may further contain other components as appropriate within a range that does not impair the effect. Examples of such other components include a coagulation-delaying component composed of a saccharide, a salt of a hydroxycarboxylic acid, etc., a component having a dispersing action composed of sodium lignin sulfonate, etc., an AE agent composed of an anionic surfactant, etc., a defoaming agent composed of an alkylene oxide compound, etc., a hardening accelerator composed of an alkanolamine, etc., a shrinkage-reducing agent composed of a polyoxyalkylene alkyl ether, etc., a tackifier composed of a cellulose ether compound, etc., a preservative composed of an isothiazoline compound, etc., a rust inhibitor composed of a nitrite, etc.
The content of the other component may be, for example, 0 to 5% by mass in terms of solid content relative to 100% by mass of the binder.
In the hydraulic composition of the present invention, the ratio of water to binder (water/binder ratio) may be appropriately set to a conventionally known ratio, and may be, for example, 25 to 70 mass%.
Examples (example)
Hereinafter, the present invention will be specifically described based on examples, but the present invention is not limited to these examples.
Water-soluble vinyl copolymers (P-1) to (P-22) and (RP-1) to (RP-2) were produced as follows. The following describes the production method of each of the water-soluble vinyl copolymers (P-1) to (P-22) and (RP-1) to (RP-2).
Production example 1 Synthesis of admixture (P-1) for Hydraulic composition
180.3g of tap water and 420.6g of α - (3-methyl-3-butenyl) - ω -hydroxy-poly (average 53 mol) ethylene oxide were charged into a reaction vessel equipped with a thermometer, a stirrer, a dropping funnel and a nitrogen inlet tube, and after stirring to uniformly dissolve, nitrogen was substituted for the atmosphere, and the temperature of the reaction system was maintained at 60℃by a warm water bath.
Next, 29.3g of a 3.5% aqueous hydrogen peroxide solution was added dropwise over 3 hours, while "an aqueous solution obtained by uniformly dissolving 29.4g of acrylic acid, 9.8g of 2-acryloyloxyethyl succinate, 29.4g of 2-hydroxyethyl acrylate in 103.4g of tap water" was added dropwise over 3 hours, while "an aqueous solution obtained by dissolving 2.0g of L-ascorbic acid and 5.9g of 3-mercaptopropionic acid in 18.2g of tap water" was added dropwise over 4 hours. Thereafter, the temperature of the reaction system was maintained at 60℃for 2 hours, and the polymerization reaction was terminated to obtain a water-soluble vinyl copolymer.
Thereafter, a 30% aqueous sodium hydroxide solution was added to the reaction system so that the pH became 5, and the concentration was adjusted to 50% with tap 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 of the water-soluble vinyl copolymer contained was 22000. The reactant was used as an admixture (P-1) for hydraulic compositions.
Production examples 2 to 11 Synthesis of additives (P-2) to (P-11) for hydraulic compositions
The same procedure as in production example 1 was repeated except that the types and amounts of the components were changed and the amounts of 3-mercaptopropionic acid were changed so as to obtain predetermined mass average molecular weights as shown in Table 1 for the admixtures (P-2) to (P-11) for hydraulic compositions of production examples 2 to 11.
PREPARATION EXAMPLE 12 Synthesis of admixture for hydraulic composition (P-12)
179.6g of tap water and 419.0g of α - (3-methyl-3-butenyl) - ω -hydroxy-poly (average 53 mol) ethylene oxide were charged into a reaction vessel equipped with a thermometer, a stirrer, a dropping funnel and a nitrogen inlet tube, and after stirring to uniformly dissolve, nitrogen was substituted into the atmosphere, and the temperature of the reaction system was maintained at 60℃by a warm water bath.
Next, 29.3g of a 3.5% aqueous hydrogen peroxide solution was added dropwise over 3 hours, while "an aqueous solution obtained by uniformly dissolving 34.1g of acrylic acid and 34.1g of 2-acryloyloxyethyl succinate in 103.0g of tap water" was added dropwise over 3 hours, and "an aqueous solution obtained by dissolving 2.0g of L-ascorbic acid and 5.9g of 3-mercaptopropionic acid in 18.2g of tap water" was added dropwise over 4 hours. Thereafter, the temperature of the reaction system was maintained at 60℃for 2 hours, and the polymerization reaction was terminated to obtain a water-soluble vinyl copolymer.
Thereafter, a 30% aqueous sodium hydroxide solution was added to the reaction system so that the pH became 5, and the concentration was adjusted to 50% with tap 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 of the water-soluble vinyl copolymer contained was 20000. The reactant was used as an admixture for hydraulic compositions (P-12).
Production examples 13 to 21 and 23 Synthesis of additives (P-13) to (P-21) and (RP-1) for hydraulic compositions
The hydraulic composition additives (P-13) to (P-21) and (RP-1) of production examples 13 to 21 and 23 were produced in the same manner as in production example 12 except that the types and amounts of the constituent units were changed and the amounts of 3-mercaptopropionic acid were changed so as to have a predetermined mass average molecular weight as shown in Table 1.
PREPARATION EXAMPLE 22 Synthesis of admixture for hydraulic composition (P-22)
323.9g of tap water and 437.7g of ethylene oxide (average 52 mol) of α -vinyl- ω -hydroxy-butene-monoxide were charged into a reaction vessel equipped with a thermometer, a stirrer, a dropping funnel and a nitrogen inlet tube, and after stirring to dissolve uniformly, the atmosphere was replaced with nitrogen, and the temperature of the reaction system was kept at 10℃by an ice-water bath. After confirming that the reaction vessel was at 10 ℃, 22.1g of acrylic acid, 2.8g of thioglycollic acid, 0.05g of ferrous sulfate heptahydrate, and 1.4g of a 35% aqueous hydrogen peroxide solution were charged into the reaction vessel.
Next, an "aqueous solution obtained by uniformly dissolving 22.7g of acrylic acid, 14.9g of 2-acryloyloxyethyl succinate and 2.4g of thioglycolic acid in 37.6g of tap water" was added dropwise over 45 minutes, and an "aqueous solution obtained by uniformly dissolving 1.0g of sodium hydroxymethanesulfinate dihydrate in 48.7g of tap water" was added dropwise over 45 minutes. Thereafter, the temperature of the reaction system was maintained at 10℃for 1 hour, and the polymerization reaction was terminated to obtain a water-soluble vinyl copolymer.
Thereafter, a 30% aqueous sodium hydroxide solution was added to the reaction system so that the pH became 5, and the concentration was adjusted to 50% with tap 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 of the water-soluble vinyl copolymer contained was 27000. The reactant was used as an admixture for hydraulic compositions (P-22).
PREPARATION EXAMPLE 24 Synthesis of admixture (RP-2) for hydraulic composition
188.1g of tap water and 439.0g of α - (3-methyl-3-butenyl) - ω -hydroxy-poly (average 53 mol) ethylene oxide were charged into a reaction vessel equipped with a thermometer, a stirrer, a dropping funnel and a nitrogen inlet tube, and after stirring to uniformly dissolve, the atmosphere was replaced with nitrogen, and the temperature of the reaction system was maintained at 60℃by a warm water bath.
Next, 29.6g of a 3.5% aqueous hydrogen peroxide solution was added dropwise over 3 hours, while "an aqueous solution obtained by uniformly dissolving 48.8g of acrylic acid in 96.4g of tap water" was added dropwise over 3 hours, while "an aqueous solution obtained by dissolving 2.0g of L-ascorbic acid and 4.9g of 3-mercaptopropionic acid in 16.0g of tap water" was added dropwise over 4 hours. Thereafter, the temperature of the reaction system was maintained at 60℃for 2 hours, and the polymerization reaction was terminated to obtain a water-soluble vinyl copolymer.
Thereafter, a 30% aqueous sodium hydroxide solution was added to the reaction system so that the pH became 5, and the concentration was adjusted to 50% with tap 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 of the water-soluble vinyl copolymer contained was 25000. The reactant was used as an admixture for hydraulic compositions (RP-2).
[ Table 1]
In Table 1, A-1 to A-5, B-1, C-1 to C-4 and D-1 to D-2 represent the following compounds, and each of the structural units 1 to 4 is formed of each compound and is a structural unit derived from each compound.
A-1: alpha- (3-methyl-3-butenyl) -omega-hydroxy-poly (average 53 moles) ethylene oxide
A-2: alpha- (3-methyl-3-butenyl) -omega-hydroxy-poly (average 80 mole) ethylene oxide
A-3: alpha- (3-methyl-3-butenyl) -omega-hydroxy-poly (average 25 moles) ethylene oxide
A-4: alpha-methallyl-omega-hydroxy-poly (average 53 moles) ethylene oxide
A-5: alpha-vinyl-omega-hydroxy-butene monoxide poly (average 52 mole) ethylene oxide
B-1: acrylic acid
C-1: succinic acid 2-acryloyloxy ethyl ester
C-2: hexahydrophthalic acid 2-acryloyloxy ethyl ester
C-3: phthalic acid 2-acryloyloxy ethyl ester
C-4: monoester of 2-hydroxyethyl acrylate and trimellitic acid
D-1: acrylic acid 2-hydroxy ethyl ester
D-2: acrylic acid methyl ester
(mass average molecular weight)
The conditions of Gel Permeation Chromatography (GPC) in measuring the mass average molecular weight of the water-soluble vinyl copolymer contained in the reaction mixture are shown below.
< measurement Condition >
The device comprises: shodex GPC-101 (manufactured by Showa electric company)
Column: OHpak SB-g+sb-804hq+sb-802.5HQ (manufactured by sho-o electric company) detector: differential Refractometer (RI)
Eluent: 50mM sodium nitrate aqueous solution
Flow rate: 0.7 mL/min
Column temperature: 40 DEG C
Sample concentration: eluent solution with sample concentration of 0.5 mass%
Standard substance: PEG/PEO (manufactured by Agilent Technologies Co., ltd.)
Examples 1 to 22 and comparative examples 1 to 2
Next, each hydraulic composition (concrete) was prepared using the additive for hydraulic compositions produced by using the formulation No.1 shown in Table 2.
Thereafter, each evaluation was performed as shown in table 3. Specifically, the amount of the admixture for hydraulic compositions used was evaluated, and slump and air content were measured. Table 3 shows the evaluation results.
The following shows a specific method for producing a hydraulic composition (concrete). Under the mixing conditions shown in Table 2, ordinary portland Cement (manufactured by Taiheiyo ceramic Co., ltd., manufactured by Mitsubishi UBE Cement Co., ltd., and SUMITOMO OSAKA CEMENT Co., ltd., density=3.16 g/cm) was charged into a 50L pan-type strong mixer in a laboratory at 20 ℃ 3 ) Binder (hydraulic binder) and Liu Sha (produced by Daikou water, density=2.57 g/cm) as aggregate 3 ) And crushed stone (Kawasaki crushed stone, density=2.68 g/cm) 3 ). The hydraulic composition admixture (see table 1) was measured as a part of the mixing water, and the AE agent "AE-300 (manufactured by the company of the bamboo oil and fat)" and the antifoaming agent "AFK-2 (manufactured by the company of the bamboo oil and fat)" were further measured as a part of the mixing water (Pu Jun city tap water) and put into a mixer so as to obtain a predetermined air amount, and mixed for 90 seconds, according to the amount shown in table 3.The hydraulic composition was prepared so that the slump immediately after mixing was 21.+ -.1 cm and the air amount was in the range of 4.5.+ -. 0.5%.
[ Table 2]
Next, the evaluation methods of the respective evaluations of the concrete are as follows.
Evaluation of the amount of admixture for Hydraulic composition
The amount of the admixture for hydraulic compositions used in the preparation of hydraulic compositions was evaluated so as to achieve a predetermined slump (0 minutes (cm)) and air amount. The smaller the amount of the admixture for hydraulic compositions used, the more excellent the effect was exhibited, and the evaluation was high and the initial dispersibility was good.
The evaluation criteria are as follows. The amount of the admixture for hydraulic compositions used was less than Cx0.20% and was evaluated as "A". The above-mentioned use amount was C.times.0.20% or more and less than 0.30% and was evaluated as "B". The above amount of use was C.times.0.30% or more, and was evaluated as "C".
Slump (cm):
slump was measured on concrete immediately after mixing (0 minutes), after mixing for 30 minutes and after mixing for 60 minutes, based on JIS A1101. Then, by the formula: (slump after 60 minutes of mixing) - (slump immediately after mixing) the difference between the slump immediately after mixing and the slump after 60 minutes of mixing (the amount of change in slump) was calculated, and the flow retention was evaluated using the amount of change. The smaller the value of the variation, the more fluidity can be maintained.
The difference (amount of change) in slump was expressed by a positive value when slump (cm) after 60 minutes of mixing was smaller than that immediately after mixing, and by a negative value when slump was larger.
The evaluation criteria are shown below. The slump immediately after mixing and the slump after mixing for 60 minutes (the amount of change in slump) were evaluated as "A" when they were less than 3cm (negative values of 0cm or less were also included). The difference between the slump immediately after mixing and the slump after mixing for 60 minutes (the amount of change in slump) was 3cm or more and less than 5cm, and was evaluated as "B". The difference between the slump immediately after mixing and the slump after mixing for 60 minutes (the amount of change in slump) was 5cm or more and less than 7cm, and was evaluated as "C". The slump immediately after mixing and the slump after mixing for 60 minutes were evaluated as "D" when the difference was 7cm or more and less than 9 cm. The slump immediately after mixing and the slump after mixing for 60 minutes were evaluated as "E" when the difference was 9cm or more.
Air amount (volume%):
the concrete immediately after mixing was measured based on JIS a 1128.
[ Table 3]
In Table 3, the amounts of the additives for hydraulic compositions used are all expressed in terms of solid content.
(results)
As shown in table 3, it was confirmed that by using the admixture for hydraulic compositions of the present example in hydraulic compositions, both excellent initial dispersibility and excellent flow retention in hydraulic compositions can be exhibited. In particular, if the content ratio of the structural unit 2 is lower than the lower limit value (2 mass%) as in comparative example 1, the amount of the additive to be used becomes large (that is, the effect cannot be obtained without using a large amount of the additive), and a result indicating poor initial dispersibility is obtained. Further, if the amount of the additive to be used is increased, hysteresis occurs. That is, since the effect of the admixture is exhibited after a lapse of a predetermined period of time and the slump is gradually increased, it is difficult to manage concrete (hydraulic composition). It is understood that the content ratio is important not only for simply containing a predetermined structural unit but also for the above-mentioned structural unit. Further, as shown in comparative example 2, it was found that the flow retention was not sufficiently obtained without the structural unit 3.
Industrial applicability
The admixture for hydraulic compositions of the present invention can be used as an admixture for hydraulic compositions such as concrete. The hydraulic composition of the present invention can be used as a hydraulic composition for concrete and the like.
Claims (7)
1. An admixture for hydraulic compositions, which comprises a water-soluble vinyl copolymer having in the molecule a structural unit 1 formed of a compound represented by the following general formula (1), a structural unit 2 formed of a compound represented by the following general formula (2), and a structural unit 3 formed of a compound represented by the following general formula (3),
assuming that the total of the constituent ratios of the structural unit 1, the structural unit 2, and the structural unit 3 is 100% by mass, the structural unit 1 is contained in a ratio of 65 to 95% by mass, the structural unit 2 is contained in a ratio of 2 to 30% by mass, the structural unit 3 is contained in a ratio of 0.1 to 25% by mass,
in the general formula (1), R 1 、R 2 、R 3 Each independently is a hydrogen atom or a methyl group, R 4 O is an oxyalkylene group of 2 to 4 carbon atoms, wherein when there are a plurality of the oxyalkylene groups, it may be 1 or 2 or more, m is an integer of 0 to 2, and n is R 4 The average addition mole number of O is 1-300,
in the general formula (2), R 5 Is a hydrogen atom or a methyl group, M 1 Is a hydrogen atom, a metal atom, ammonium or an organic amine,
in the general formula (3), R 6 Is a hydrogen atom or methyl group, R 7 O is an oxyalkylene group having 2 to 4 carbon atoms, wherein when there are a plurality of the oxyalkylene groups, the number of the oxyalkylene groups may be 1 or 2 or more, R 8 Is a chain alkylene group having 1 to 22 carbon atoms, a cyclic alkylene group having 3 to 10 carbon atoms or an aryl group having 6 to 22 carbon atoms, and p is R 7 O has an average addition mole number of 1 to 5, q is an integer of 0 to 2, M 2 、M 3 Each independently is a hydrogen atom, a metal atom, ammonium or an organic amine.
2. The admixture for hydraulic compositions according to claim 1, wherein the compound represented by the general formula (3) forming the structural unit 3 contains a condensate of 2-hydroxyethyl (meth) acrylate and a di-to tetracarboxylic anhydride.
3. The admixture for hydraulic compositions according to claim 1 or 2, wherein the compound represented by the general formula (3) forming the structural unit 3 contains at least one selected from the group consisting of 2- (meth) acryloyloxyethyl succinate, 2- (meth) acryloyloxyethyl hexahydrophthalate and 2- (meth) acryloyloxyethyl phthalate.
4. The admixture for hydraulic compositions according to any one of claims 1 to 3, wherein the water-soluble vinyl copolymer further comprises a structural unit 4 formed of a compound represented by the following general formula (4) in a molecule,
assuming that the total of the constituent ratios of the structural unit 1, the structural unit 2, the structural unit 3, and the structural unit 4 is 100% by mass, the structural unit 1 is contained in a ratio of 65 to 95% by mass, the structural unit 2 is contained in a ratio of 2 to 30% by mass, the structural unit 3 is contained in a ratio of 0.1 to 10% by mass, and the structural unit 4 is contained in a ratio of 0.1 to 15% by mass,
in the general formula (4), R 9 Is a hydrogen atom or methyl group, R 10 O is an oxyalkylene group of 2 to 4 carbon atoms, wherein when there are a plurality of the oxyalkylene groups, it may be 1 or 2 or more kinds alone, and R is R 10 The average addition mole number of O is 0-10, R 11 Is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, wherein r=0, R 11 Is an alkyl group having 1 to 5 carbon atoms.
5. The admixture for hydraulic compositions according to claim 4, wherein the compound represented by the general formula (4) forming the structural unit 4 contains 2-hydroxyethyl (meth) acrylate.
6. The admixture for hydraulic compositions according to any one of claims 1 to 5, wherein the water-soluble vinyl copolymer has a mass average molecular weight of 5000 to 100000.
7. A hydraulic composition comprising the admixture for a hydraulic composition according to any one of claims 1 to 6.
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| Application Number | Priority Date | Filing Date | Title |
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| JP2021180118A JP7099767B1 (en) | 2021-11-04 | 2021-11-04 | Admixture for hydraulic composition and hydraulic composition |
| JP2021-180118 | 2021-11-04 |
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| CN116063021A true CN116063021A (en) | 2023-05-05 |
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| CN (1) | CN116063021A (en) |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101679120A (en) * | 2007-05-22 | 2010-03-24 | 花王株式会社 | Dispersion maintaining agent for hydraulic composition |
| CN111051265A (en) * | 2017-09-12 | 2020-04-21 | 竹本油脂株式会社 | Dispersion maintaining agent for hydraulic composition |
| CN112969672A (en) * | 2018-11-13 | 2021-06-15 | 竹本油脂株式会社 | Additive for hydraulic composition and hydraulic composition |
| JPWO2020115788A1 (en) * | 2018-12-03 | 2021-09-27 | 竹本油脂株式会社 | Additives for hydraulic compositions and hydraulic compositions |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN106336485B (en) * | 2016-08-12 | 2018-06-01 | 河北三楷深发科技股份有限公司 | A kind of low damage poly carboxylic acid series water reducer and preparation method thereof that collapses of anti-chamotte mould |
| WO2020100212A1 (en) * | 2018-11-13 | 2020-05-22 | 竹本油脂株式会社 | Method for manufacturing additive for hydraulic composition |
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- 2021-11-04 JP JP2021180118A patent/JP7099767B1/en active Active
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101679120A (en) * | 2007-05-22 | 2010-03-24 | 花王株式会社 | Dispersion maintaining agent for hydraulic composition |
| CN111051265A (en) * | 2017-09-12 | 2020-04-21 | 竹本油脂株式会社 | Dispersion maintaining agent for hydraulic composition |
| CN112969672A (en) * | 2018-11-13 | 2021-06-15 | 竹本油脂株式会社 | Additive for hydraulic composition and hydraulic composition |
| JPWO2020115788A1 (en) * | 2018-12-03 | 2021-09-27 | 竹本油脂株式会社 | Additives for hydraulic compositions and hydraulic compositions |
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| JP2023068793A (en) | 2023-05-18 |
| JP7099767B1 (en) | 2022-07-12 |
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