CN112175148B - Crosslinking type early-strength carboxylic acid water reducing agent, and preparation method and application thereof - Google Patents
Crosslinking type early-strength carboxylic acid water reducing agent, and preparation method and application thereof Download PDFInfo
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- CN112175148B CN112175148B CN202011004390.1A CN202011004390A CN112175148B CN 112175148 B CN112175148 B CN 112175148B CN 202011004390 A CN202011004390 A CN 202011004390A CN 112175148 B CN112175148 B CN 112175148B
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- polyoxyethylene ether
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 103
- 239000003638 chemical reducing agent Substances 0.000 title claims abstract description 69
- 238000004132 cross linking Methods 0.000 title claims abstract description 61
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- 150000001732 carboxylic acid derivatives Chemical class 0.000 title claims abstract description 13
- 229920005646 polycarboxylate Polymers 0.000 claims abstract description 60
- 229940051841 polyoxyethylene ether Drugs 0.000 claims abstract description 48
- 229920000056 polyoxyethylene ether Polymers 0.000 claims abstract description 48
- 239000000178 monomer Substances 0.000 claims abstract description 45
- 125000003342 alkenyl group Chemical group 0.000 claims abstract description 42
- 239000008030 superplasticizer Substances 0.000 claims abstract description 41
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims abstract description 35
- 239000003431 cross linking reagent Substances 0.000 claims abstract description 31
- 239000003999 initiator Substances 0.000 claims abstract description 21
- 239000000243 solution Substances 0.000 claims description 46
- 238000003756 stirring Methods 0.000 claims description 41
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 25
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical group O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims description 21
- 239000011259 mixed solution Substances 0.000 claims description 21
- SZHIIIPPJJXYRY-UHFFFAOYSA-M sodium;2-methylprop-2-ene-1-sulfonate Chemical group [Na+].CC(=C)CS([O-])(=O)=O SZHIIIPPJJXYRY-UHFFFAOYSA-M 0.000 claims description 20
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 18
- 239000002253 acid Substances 0.000 claims description 18
- 150000001990 dicarboxylic acid derivatives Chemical class 0.000 claims description 17
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 14
- 238000000034 method Methods 0.000 claims description 12
- 239000004593 Epoxy Substances 0.000 claims description 11
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims description 11
- 229910000077 silane Inorganic materials 0.000 claims description 11
- 229960001922 sodium perborate Drugs 0.000 claims description 9
- YKLJGMBLPUQQOI-UHFFFAOYSA-M sodium;oxidooxy(oxo)borane Chemical compound [Na+].[O-]OB=O YKLJGMBLPUQQOI-UHFFFAOYSA-M 0.000 claims description 9
- 229920002873 Polyethylenimine Polymers 0.000 claims description 8
- 150000001718 carbodiimides Chemical class 0.000 claims description 8
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 7
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 claims description 3
- 150000002762 monocarboxylic acid derivatives Chemical class 0.000 claims 3
- ZZZCUOFIHGPKAK-UHFFFAOYSA-N D-erythro-ascorbic acid Natural products OCC1OC(=O)C(O)=C1O ZZZCUOFIHGPKAK-UHFFFAOYSA-N 0.000 claims 1
- 229930003268 Vitamin C Natural products 0.000 claims 1
- 235000019154 vitamin C Nutrition 0.000 claims 1
- 239000011718 vitamin C Substances 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 13
- 230000000740 bleeding effect Effects 0.000 abstract description 10
- 230000005764 inhibitory process Effects 0.000 abstract description 4
- 230000001133 acceleration Effects 0.000 abstract description 2
- 239000004568 cement Substances 0.000 description 28
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 15
- 230000015271 coagulation Effects 0.000 description 13
- 238000005345 coagulation Methods 0.000 description 13
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 12
- 230000036571 hydration Effects 0.000 description 12
- 238000006703 hydration reaction Methods 0.000 description 12
- 150000002763 monocarboxylic acids Chemical class 0.000 description 12
- 230000001737 promoting effect Effects 0.000 description 12
- 238000006243 chemical reaction Methods 0.000 description 10
- 239000003513 alkali Substances 0.000 description 8
- 230000009286 beneficial effect Effects 0.000 description 8
- 239000000126 substance Substances 0.000 description 8
- 150000002148 esters Chemical group 0.000 description 7
- 239000000203 mixture Substances 0.000 description 7
- -1 alkenyl sulfonate Chemical compound 0.000 description 6
- 238000010276 construction Methods 0.000 description 6
- 230000001976 improved effect Effects 0.000 description 5
- 230000008569 process Effects 0.000 description 5
- 230000009467 reduction Effects 0.000 description 5
- 239000002202 Polyethylene glycol Substances 0.000 description 4
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 4
- 239000012456 homogeneous solution Substances 0.000 description 4
- 230000014759 maintenance of location Effects 0.000 description 4
- 229920001223 polyethylene glycol Polymers 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 4
- 150000001412 amines Chemical class 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 239000006185 dispersion Substances 0.000 description 3
- 230000007062 hydrolysis Effects 0.000 description 3
- 238000006460 hydrolysis reaction Methods 0.000 description 3
- 239000004615 ingredient Substances 0.000 description 3
- QVDTXNVYSHVCGW-ONEGZZNKSA-N isopentenol Chemical compound CC(C)\C=C\O QVDTXNVYSHVCGW-ONEGZZNKSA-N 0.000 description 3
- 238000004904 shortening Methods 0.000 description 3
- BYDRTKVGBRTTIT-UHFFFAOYSA-N 2-methylprop-2-en-1-ol Chemical compound CC(=C)CO BYDRTKVGBRTTIT-UHFFFAOYSA-N 0.000 description 2
- WCASXYBKJHWFMY-UHFFFAOYSA-N crotyl alcohol Chemical compound CC=CCO WCASXYBKJHWFMY-UHFFFAOYSA-N 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000004576 sand Substances 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 229910001294 Reinforcing steel Inorganic materials 0.000 description 1
- 229960005070 ascorbic acid Drugs 0.000 description 1
- 230000021523 carboxylation Effects 0.000 description 1
- 238000006473 carboxylation reaction Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 239000011243 crosslinked material Substances 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 239000003651 drinking water Substances 0.000 description 1
- 235000020188 drinking water Nutrition 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000010881 fly ash Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 229910017053 inorganic salt Inorganic materials 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- PHTQWCKDNZKARW-UHFFFAOYSA-N isoamylol Chemical compound CC(C)CCO PHTQWCKDNZKARW-UHFFFAOYSA-N 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- 230000033116 oxidation-reduction process Effects 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 125000000542 sulfonic acid group Chemical group 0.000 description 1
Classifications
-
- 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
-
- 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
- C04B24/2688—Copolymers containing at least three different monomers
- C04B24/2694—Copolymers containing at least three different monomers containing polyether side chains
-
- 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
- C08F2/00—Processes of polymerisation
- C08F2/38—Polymerisation using regulators, e.g. chain terminating agents, e.g. telomerisation
-
- 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
- C08F4/00—Polymerisation catalysts
- C08F4/40—Redox systems
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/24—Crosslinking, e.g. vulcanising, of macromolecules
- C08J3/246—Intercrosslinking of at least two polymers
-
- 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
- C04B2103/00—Function or property of ingredients for mortars, concrete or artificial stone
- C04B2103/30—Water reducers, plasticisers, air-entrainers, flow improvers
- C04B2103/302—Water reducers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2351/00—Characterised by the use of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers
- C08J2351/08—Characterised by the use of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers grafted on to macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
- Y02W30/50—Reuse, recycling or recovery technologies
- Y02W30/91—Use of waste materials as fillers for mortars or concrete
Abstract
The invention provides a crosslinking type early strength carboxylic acid water reducing agent, a preparation method and application thereof. The cross-linking type early-strength polycarboxylate water reducer is prepared from multiple components, wherein the components comprise alkenyl polyoxyethylene ether, unsaturated carboxylic acid monomers, a molecular weight regulator, an initiator, a reducing agent and a carboxyl cross-linking agent, and the mass ratio of the carboxyl cross-linking agent to the alkenyl polyoxyethylene ether is 0.5-1.5: 100. The cross-linking type early-strength polycarboxylate superplasticizer has the effects of high water reducing rate, bleeding inhibition, slow release and slump retaining in a short time, setting acceleration, early strength and the like, and is simple in preparation process, low in cost, environment-friendly and energy-saving.
Description
Technical Field
The invention relates to the field of concrete water reducing agents, in particular to a cross-linking type early-strength carboxylic acid water reducing agent, and a preparation method and application thereof.
Background
Generally, the early strength of concrete is increased primarily by increasing the early hydration level of the cement. The polycarboxylic acid water reducing agent has the advantages of high water reducing rate, good concrete workability, small slump loss, low chloride ion and alkali content, small concrete shrinkage, environment-friendly production and application processes and no harm to human bodies, so the polycarboxylic acid water reducing agent is favored by the industry. In the prior art, the early strength of concrete is improved by compounding the early strength agent in the polycarboxylic acid water reducing agent, but the early strength agent has certain problems in the current application, for example, inorganic salt early strength agents contain Cl-And alkali, the problems of rust removal and corrosion of the reinforcing steel bars are easily caused. At present, part of early-strength polycarboxylate superplasticizers are used for producing concrete prefabricated parts and requiring preparation of early-strength concrete, but the early-strength concrete exists in the preparation processThe problems of high difficulty in esterification and ester exchange, complex process, high cost, easy bleeding, over-quick slump loss and the like during the preparation of concrete.
Therefore, the early strength polycarboxylate superplasticizer which has simple preparation process and low cost, and has the effects of high water reducing rate, bleeding inhibition, coagulation promotion, early strength and the like is needed.
Disclosure of Invention
The invention aims to provide a cross-linking type early strength polycarboxylate water reducer which has the advantages of simple preparation process, low cost, high water reducing rate, bleeding inhibition, coagulation promotion, early strength and the like.
In order to achieve the purpose, the invention provides a crosslinking type early-strength polycarboxylate superplasticizer which is prepared from multiple components, wherein the components comprise alkenyl polyoxyethylene ether, an unsaturated carboxylic acid monomer, a molecular weight regulator, an initiator, a reducing agent and a carboxyl crosslinking agent, and the mass ratio of the carboxyl crosslinking agent to the alkenyl polyoxyethylene ether is 0.5-1.5: 100.
Preferably, the mass ratio of the unsaturated carboxylic acid monomer to the alkenyl polyoxyethylene ether is 6-12: 100.
Preferably, the mass ratio of the molecular weight regulator to the alkenyl polyoxyethylene ether is 2-5: 100.
Preferably, the mass ratio of the initiator to the alkenyl polyoxyethylene ether is 0.6-1.6: 100.
Preferably, the mass ratio of the reducing agent to the alkenyl polyoxyethylene ether is 0.2-0.6: 100.
Preferably, the unsaturated carboxylic acid monomers include unsaturated monocarboxylic acid monomers and unsaturated dicarboxylic acid monomers; the unsaturated monocarboxylic acid monomer is preferably acrylic acid, and the unsaturated dicarboxylic acid monomer is preferably maleic anhydride; the mass ratio of the acrylic acid to the maleic anhydride is 5-10: 1-2. The addition of the maleic anhydride is beneficial to increasing the density of main chain carboxyl, improving the water reducing rate and facilitating the subsequent crosslinking reaction.
Preferably, the molecular weight of the alkenyl polyoxyethylene ether is 3000-5000.
Preferably, the alkenyl polyoxyethylene ether is one of methallyl alcohol polyoxyethylene ether (HPEG), isopentenol polyoxyethylene ether (TPEG) and ethylene glycol monovinyl polyethylene glycol ether (EPEG). The invention adopts the alkenyl polyoxyethylene ether macromonomer with larger molecular weight to prepare the crosslinking type early strength polycarboxylate water reducer, and the longer side chain is beneficial to increasing the dispersion property of the water reducer, accelerating the hydration of cement and promoting the development of early strength of the cement.
Preferably, the molecular weight regulator is sodium methallyl sulfonate. The invention adopts alkenyl sulfonate as a molecular weight regulator to prepare the cross-linking type early-strength polycarboxylate superplasticizer, and is beneficial to introducing sulfonate with an early-strength function.
Preferably, the initiator is one or two of hydrogen peroxide, ammonium persulfate and sodium perborate.
Preferably, the reducing agent is vitamin c (vc). VC is selected as a reducing agent, so that the cost is lower than that of other reducing agents, and the method is safe and environment-friendly.
Preferably, the carboxyl cross-linking agent is one or two of polyaluminium, polyethylenimine, carbodiimide, and epoxy silane. The invention adopts organic amine or aluminum salt compound as a cross-linking agent to avoid Cl-Or harmful ingredients such as alkali and the like are brought in, partial carboxyl polymer can be controlled to be crosslinked at normal temperature, the hydrolysis speed is higher than that of a normal ester polycarboxylic acid slow-release water reducing agent under the strong alkali condition, and the hydrolyzed ester polycarboxylic acid slow-release water reducing agent has the effect of accelerating the coagulation of cement and promotes the development of the early strength of concrete.
The invention also provides a preparation method of the crosslinking type early strength polycarboxylate superplasticizer, which comprises the following steps: 102, adding a certain amount of unsaturated monocarboxylic acid monomer into a certain amount of pure water, and uniformly stirring to obtain a uniform solution A; 104, adding a certain amount of molecular weight regulator and a certain amount of reducing agent into a certain amount of pure water, and uniformly stirring to obtain a uniform solution B; 106, adding a certain amount of alkenyl polyoxyethylene ether into a certain amount of pure water, adding a certain amount of unsaturated dicarboxylic acid monomer, stirring until the unsaturated dicarboxylic acid monomer is dissolved, adding a certain amount of initiator at a certain temperature, and stirring for reacting for a period of time; 108, simultaneously dripping the uniform solution A and the uniform solution B into the mixed solution obtained in the step 106 at a certain temperature, and reacting for a certain time after finishing dripping; and step 110, adding water to dilute the mixed solution obtained in the step 108, dropwise adding a carboxyl cross-linking agent while stirring, and reacting for a certain time after the dropwise adding is finished to obtain the cross-linking type early-strength polycarboxylate superplasticizer.
Preferably, the mass ratio of the unsaturated monocarboxylic acid monomer, the unsaturated dicarboxylic acid monomer, the molecular weight regulator, the reducing agent, the initiator, the carboxyl cross-linking agent and the alkenyl polyoxyethylene ether is 5-10:1-2:2-5:0.2-0.6:0.6-1.6:0.5-1.5: 100. The cross-linking type early strength polycarboxylate superplasticizer is prepared by selecting a specific grafting proportion, so that the water-reducing rate is high, and the hydration degree of cement can be effectively improved.
Preferably, the molecular weight of the alkenyl polyoxyethylene ether is 3000-5000.
Preferably, the alkenyl polyoxyethylene ether is one of methallyl alcohol polyoxyethylene ether (HPEG), isopentenol polyoxyethylene ether (TPEG) and ethylene glycol monovinyl polyethylene glycol ether (EPEG).
Preferably, the unsaturated monocarboxylic acid monomer is acrylic acid; the unsaturated dicarboxylic acid monomer is maleic anhydride; the mass ratio of the acrylic acid to the maleic anhydride is 5-10: 1-2.
Preferably, the molecular weight regulator is sodium methallyl sulfonate.
Preferably, the reducing agent is VC.
Preferably, the initiator is one or two of hydrogen peroxide, ammonium persulfate and sodium perborate.
Preferably, the carboxyl cross-linking agent is one or two of polyaluminium, polyethylenimine, carbodiimide, and epoxy silane.
Preferably, in step 102, the mass ratio of the unsaturated monocarboxylic acid monomer to pure water is 1: 2.
The invention adopts alkenyl polyoxyethylene ether with large molecular weight and alkenyl monomer with sulfonic acid group as molecular weight regulator, utilizes redox system to copolymerize with monomers such as acrylic acid and maleic anhydride at normal temperature, and then adds crosslinking component with coagulation accelerating and early strength functions to partially crosslink at normal temperature, thus preparing the crosslinking type early strength polycarboxylate superplasticizer. On the premise of ensuring higher water reduction, part of macromolecular cross-linking substances have a water retention effect in the early stage, and can effectively inhibit early-stage bleeding, and the cross-linking substances are quickly decomposed into components with dispersing power and a coagulation promoting effect in a cement strong alkaline environment, so that the polycarboxylic acid water reducing agent has the construction performance of slump retention within 30 minutes, thereby promoting cement hydration, shortening the setting time of concrete, improving the early strength of the concrete, and effectively ensuring the stable development of later strength.
Preferably, in step 104, the mass ratio of the sum of the masses of the molecular weight regulator and the reducing agent to pure water is 1: 20.
Preferably, in step 106, the mass ratio of the alkenyl polyoxyethylene ether to the pure water is 1: 0.78.
Preferably, in step 106, the temperature at which the initiator is added is 15-25 ℃.
Preferably, in step 106, the reaction is stirred for 5-10 min.
Preferably, the temperature of the uniform solution A and the uniform solution B added dropwise in step 108 is 20-35 ℃.
Preferably, in step 108, the uniform solution A and the uniform solution B are dropwise added at a constant speed and are dropwise added within 1.5-2 h.
Preferably, in step 108, the homogeneous solution A and the homogeneous solution B are reacted for 1 to 2 hours after the dropwise addition.
Preferably, in step 110, the mixed solution obtained in step 108 is diluted with water to a mass concentration of 15-25%.
Preferably, in step 110, the mass concentration of the carboxyl cross-linking agent is 5%.
Preferably, in step 110, the dropwise addition of the carboxyl cross-linking agent is performed at a constant speed and is completed within 0.5 h.
Preferably, in step 110, the reaction is carried out for 1.5h after the carboxyl cross-linking agent is added dropwise.
The invention also provides application of the crosslinking type early-strength polycarboxylate superplasticizer in engineering. On the premise of ensuring higher water reduction, part of macromolecular cross-linking substances have a water retention effect in the early stage, and can effectively inhibit early-stage bleeding, and the cross-linking substances are quickly decomposed into components with dispersing power and a coagulation promoting effect in a cement strong alkaline environment, so that the cement early-strength polycarboxylate water reducer has the construction performance of slump retention in 30 minutes, thereby promoting the cement hydration, shortening the setting time of concrete, improving the early strength of concrete, and effectively ensuring the stable development of later strength.
The invention adopts the alkenyl polyoxyethylene ether macromonomer with larger molecular weight to prepare the cross-linked early-strength polycarboxylate water reducer, and the longer side chain is beneficial to increasing the dispersion property of the water reducer, accelerating the hydration of cement and promoting the development of early strength of the cement; the alkenyl sulfonate is adopted as a molecular weight regulator, which is beneficial to introducing the sulfonate with early strength function; organic amine or aluminum salt compounds are adopted as a crosslinking agent to avoid Cl-Or harmful ingredients such as alkali and the like are brought in, partial carboxyl polymer can be controlled to be crosslinked at normal temperature, the hydrolysis speed is higher than that of a normal ester polycarboxylic acid slow-release water reducing agent under the strong alkali condition, and the hydrolyzed ester polycarboxylic acid slow-release water reducing agent has the effect of accelerating the coagulation of cement and promotes the development of the early strength of concrete.
The invention has the beneficial effects that:
(1) the cross-linking type early strength polycarboxylate superplasticizer is prepared by selecting a specific grafting proportion, so that the water-reducing rate is high, and the hydration degree of cement can be effectively improved;
(2) in the cement alkaline environment, the cross-linked material can be quickly hydrolyzed to release carboxyl and coagulation promoting components, so that the cross-linked early-strength polycarboxylate superplasticizer has certain slump retaining property, has a coagulation promoting effect to accelerate cement hydration, and effectively improves the early strength of concrete;
(3) the preparation method of the cross-linking type early strength polycarboxylate superplasticizer is carried out at normal temperature in the whole process, and has the advantages of simple preparation process, low cost, environmental protection and energy conservation;
(4) the cross-linking type early-strength polycarboxylate superplasticizer disclosed by the invention has the characteristics or effects of high water reduction, water bleeding inhibition, slow release and slump retaining in a short time, setting acceleration, concrete early strength improvement and the like, can be suitable for various construction projects with early-strength requirements, and has a remarkable economic effect.
Detailed Description
The terms as used herein:
"prepared from … …" is synonymous with "comprising". As used herein, the terms "comprises," "comprising," "includes," "including," "has," "having," "contains" or any other variation thereof, are intended to cover a non-exclusive inclusion. For example, a composition, process, method, article, or apparatus that comprises a list of elements is not necessarily limited to only those elements but may include other elements not expressly listed or inherent to such composition, process, method, article, or apparatus.
The conjunction "consisting of … …" excludes any unspecified elements, steps or components. If used in a claim, the phrase is intended to claim as closed, meaning that it does not contain materials other than those described, except for the conventional impurities associated therewith. When the phrase "consisting of … …" appears in a clause of the subject matter of the claims rather than immediately after the subject matter, it defines only the elements described in the clause; other elements are not excluded from the claims as a whole.
When an amount, concentration, or other value or parameter is expressed as a range, preferred range, or range defined by a list of upper preferable values and lower preferable values, this is to be understood as specifically disclosing all ranges formed from any pair of any upper range limit or preferred value and any lower range limit or preferred value, regardless of whether ranges are separately disclosed. For example, when the range "1 ~ 5" is disclosed, the ranges described should be construed to include the ranges "1 ~ 4", "1 ~ 3", "1 ~ 2 and 4 ~ 5", "1 ~ 3 and 5", and the like. When a range of values is described herein, unless otherwise stated, the range is intended to include the endpoints thereof and all integers and fractions within the range.
In these examples, the parts and percentages are by mass unless otherwise indicated.
"part by mass" means a basic unit of measure indicating a mass ratio of a plurality of components, and 1 part may represent any unit mass, for example, 1g or 2.689 g. If the parts by mass of the component A are a parts and the parts by mass of the component B are B parts, the mass ratio of the component A to the component B is expressed as a: b. alternatively, the mass of the A component is aK and the mass of the B component is bK (K is an arbitrary number, and represents a multiple factor). It is unmistakable that, unlike the parts by mass, the sum of the parts by mass of all the components is not limited to 100 parts.
In the present invention, "step 102", "step 104", etc. are used merely as step numbers for explaining details of each step, and do not limit the sequence of the steps.
"and/or" is used to indicate that one or both of the illustrated conditions may occur, e.g., a and/or B includes (a and B) and (a or B).
The invention provides a cross-linking type early-strength polycarboxylate water reducer which is prepared from multiple components, wherein the components comprise alkenyl polyoxyethylene ether, an unsaturated carboxylic acid monomer, a molecular weight regulator, an initiator, a reducing agent and a carboxyl cross-linking agent, and the mass ratio of the carboxyl cross-linking agent to the alkenyl polyoxyethylene ether is 0.5-1.5: 100; the mass ratio of the unsaturated carboxylic acid monomer to the alkenyl polyoxyethylene ether is 6-12: 100; the mass ratio of the molecular weight regulator to the alkenyl polyoxyethylene ether is 2-5: 100; the mass ratio of the initiator to the alkenyl polyoxyethylene ether is 0.6-1.6: 100; the mass ratio of the reducing agent to the alkenyl polyoxyethylene ether is 0.2-0.6: 100.
As a preferred embodiment, the molecular weight of the alkenyl polyoxyethylene ether is 3000-5000. The alkenyl polyoxyethylene ether is one of methyl allyl alcohol polyoxyethylene ether (HPEG), isoamylol polyoxyethylene ether (TPEG) and ethylene glycol monovinyl polyethylene glycol ether (EPEG); the unsaturated carboxylic acid monomer comprises an unsaturated monocarboxylic acid monomer and an unsaturated dicarboxylic acid monomer; the unsaturated monocarboxylic acid monomer is acrylic acid, and the unsaturated dicarboxylic acid monomer is maleic anhydride; the molecular weight regulator is sodium methallyl sulfonate; the initiator is one or two of hydrogen peroxide, ammonium persulfate and sodium perborate; the reducing agent is VC; the carboxyl cross-linking agent is one or two of polyaluminium, polyethylenimine, carbodiimide and epoxy silane.
As a preferred embodiment, the mass ratio of acrylic acid to maleic anhydride is 5-10: 1-2.
The invention adopts the alkenyl polyoxyethylene ether macromonomer with larger molecular weight to prepare the cross-linked early-strength polycarboxylate water reducer, and the longer side chain is beneficial to increasing the dispersion property of the water reducer, accelerating the hydration of cement and promoting the development of early strength of the cement; the alkenyl sulfonate is adopted as a molecular weight regulator, which is beneficial to introducing the sulfonate with early strength function; organic amine or aluminum salt compound is adopted as a crosslinking agent to avoid Cl-Or harmful ingredients such as alkali and the like are brought in, partial carboxyl polymer can be controlled to be crosslinked at normal temperature, the hydrolysis speed is higher than that of a normal ester polycarboxylic acid slow-release water reducing agent under the strong alkali condition, and the hydrolyzed ester polycarboxylic acid slow-release water reducing agent has the effect of accelerating the coagulation of cement and promotes the development of the early strength of concrete.
The invention also provides a preparation method of the crosslinking type early strength polycarboxylate superplasticizer, which comprises the following steps:
102, adding a certain amount of unsaturated monocarboxylic acid monomer into a certain amount of pure water, and uniformly stirring to obtain a uniform solution A;
104, adding a certain amount of molecular weight regulator and a certain amount of reducing agent into a certain amount of pure water, and uniformly stirring to obtain a uniform solution B;
106, adding a certain amount of alkenyl polyoxyethylene ether into a certain amount of pure water, adding a certain amount of unsaturated dicarboxylic acid monomer, stirring until the unsaturated dicarboxylic acid monomer is dissolved, adding a certain amount of initiator at a certain temperature, and stirring for reacting for a period of time;
108, simultaneously dripping the uniform solution A and the uniform solution B into the mixed solution obtained in the step 106 at a certain temperature, and reacting for a certain time after finishing dripping;
and step 110, adding water to dilute the mixed solution obtained in the step 108, dropwise adding a carboxyl cross-linking agent while stirring, and reacting for a certain time after the dropwise adding is finished to obtain the cross-linking type early-strength polycarboxylate superplasticizer.
As a preferable embodiment, the mass ratio of the unsaturated monocarboxylic acid monomer, the unsaturated dicarboxylic acid monomer, the molecular weight regulator, the reducing agent, the initiator, the carboxyl group cross-linking agent and the alkenyl polyoxyethylene ether is 5-10:1-2:2-5:0.2-0.6:0.6-1.6:0.5-1.5: 100. The cross-linking type early-strength polycarboxylate superplasticizer is prepared by selecting a specific grafting proportion, so that the water-reducing rate is high, and the hydration degree of cement can be effectively improved.
As a preferred embodiment, the molecular weight of the alkenyl polyoxyethylene ether is 3000-5000. The alkenyl polyoxyethylene ether is one of methyl allyl alcohol polyoxyethylene ether (HPEG), isopentenol polyoxyethylene ether (TPEG) and ethylene glycol monovinyl polyethylene glycol ether (EPEG); the unsaturated monocarboxylic acid monomer is acrylic acid; the unsaturated dicarboxylic acid monomer is maleic anhydride; the molecular weight regulator is sodium methallyl sulfonate; the reducing agent is VC; the initiator is one or two of hydrogen peroxide, ammonium persulfate and sodium perborate; the carboxyl cross-linking agent is one or two of polyaluminium, polyethylenimine, carbodiimide and epoxy silane.
In a preferred embodiment, in step 102, the mass ratio of the unsaturated monocarboxylic acid monomer to pure water is 1: 2.
The embodiment of the invention adopts alkenyl polyoxyethylene ether with large molecular weight and alkenyl monomer with sulfonate as molecular weight regulator, utilizes an oxidation-reduction system to copolymerize with monomers such as acrylic acid and maleic anhydride at normal temperature, and then adds a crosslinking component with coagulation accelerating and early strength functions to partially crosslink at normal temperature, thus preparing the crosslinking type early strength polycarboxylate water reducer. On the premise of ensuring higher water reduction, part of macromolecular cross-linking substances have a water retention effect in the early stage, and can effectively inhibit early-stage bleeding, and the cross-linking substances are quickly decomposed into components with dispersing power and a coagulation promoting effect in a cement strong alkaline environment, so that the polycarboxylic acid water reducing agent has the construction performance of slump retention within 30 minutes, thereby promoting cement hydration, shortening the setting time of concrete, improving the early strength of the concrete, and effectively ensuring the stable development of later strength.
In a preferred embodiment, in step 104, the mass ratio of the sum of the masses of the molecular weight modifier and the reducing agent to pure water is 1: 20.
In a preferred embodiment, in step 106, the mass ratio of the alkenyl polyoxyethylene ether to the pure water is 1: 0.78; the temperature for adding the initiator is 15-25 ℃; adding the initiator, and stirring for reaction for 5-10 min. In step 106, the alkenyl polyoxyethylene ether is mixed with pure water, then the unsaturated dicarboxylic acid monomer is added, the mixture is uniformly stirred, then the initiator is added, and the mixture is stirred for reaction, so that the method is favorable for pre-initiating the monomer with low activity.
In a preferred embodiment, the temperature of the uniform solution A and the uniform solution B is 20-35 ℃ in step 108; dropwise adding the uniform solution A and the uniform solution B at a constant speed, and finishing dropwise adding within 1.5-2 h; after the uniform solution A and the uniform solution B are added, the reaction is carried out for 1 to 2 hours. In step 108 of the present invention, the rate of polymerization is controlled by controlling the dropping rate of the homogeneous solution A and the homogeneous solution B.
In a preferred embodiment, in step 110, the mixed solution obtained in step 108 is diluted with water to a mass concentration of 15-25%; the mass concentration of the carboxyl cross-linking agent is 5%; dropwise adding the carboxyl crosslinking agent at a constant speed, and finishing dropwise adding within 0.5 h; and reacting for 1.5h after the carboxyl cross-linking agent is added dropwise. In step 110 of the invention, the mixed solution obtained in step 108 is diluted with water and then added with a carboxyl cross-linking agent, so that the carboxyl cross-linking agent and the polymer carboxyl in the mixed solution obtained in step 108 undergo a partial cross-linking reaction at normal temperature, and the speed of the carboxyl cross-linking reaction is controlled by controlling the dropping speed of the carboxyl cross-linking agent, thereby obtaining the cross-linking type early strength polycarboxylic acid water reducer of the invention.
The third embodiment of the invention provides application of the crosslinking type early-strength polycarboxylate superplasticizer in engineering. On the premise of ensuring higher water reduction, part of macromolecular cross-linking substances have a water retention effect in the early stage, and can effectively inhibit early-stage bleeding, and the cross-linking substances are quickly decomposed into dispersing carboxylic acid and a component with a coagulation promoting effect in a cement strong alkaline environment, so that after the cement has the construction performance of slump retention within 30 minutes, cement hydration is promoted, the setting time of concrete is shortened, the early strength of the concrete is improved, the stable development of the later strength is effectively ensured, and the cross-linking type early-strength polycarboxylate water reducer is suitable for various construction projects with early strength requirements and has a remarkable economic effect.
Embodiments of the present invention will be described in detail below with reference to specific examples, but those skilled in the art will appreciate that the following examples are only illustrative of the present invention and should not be construed as limiting the scope of the present invention. The examples, in which specific conditions are not specified, were conducted under conventional conditions or conditions recommended by the manufacturer. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products available commercially.
Example 1
The embodiment provides a crosslinking type early strength polycarboxylate superplasticizer which is prepared from the following components: 100 parts of HPEG with molecular weight of 3000, 6.8 parts of acrylic acid, 1.2 parts of maleic anhydride, 0.6 part of hydrogen peroxide with mass concentration of 27.5%, 2 parts of sodium methallyl sulfonate, 0.6 part of VC and 1 part of polyaluminium.
The cross-linking type early strength polycarboxylate superplasticizer is prepared by the following steps:
(1) adding 6.8 parts by weight of acrylic acid into 2 times of pure water by weight, and uniformly stirring to obtain a uniform solution A;
(2) adding 2 parts by weight of sodium methallyl sulfonate and 0.6 part by weight of VC into pure water with the weight being 20 times that of the sodium methallyl sulfonate, and uniformly stirring to obtain a uniform solution B;
(3) adding 100 parts by weight of HPEG into 0.78 times of pure water by weight, adding 1.2 parts by weight of maleic anhydride, stirring until the mixture is dissolved, adding 0.6 part by weight of hydrogen peroxide with the mass concentration of 27.5% at the temperature of 20 ℃, and stirring for reacting for 5 min;
(4) uniformly dripping the uniform solution A obtained in the step (1) and the uniform solution B obtained in the step (2) into the mixed solution obtained in the step (3) at 25 ℃, and continuously reacting for 1 hour after finishing dripping within 1.5 hours;
(5) and (5) adding water to dilute the mixed solution obtained in the step (4) until the mass concentration is 20%, dropwise adding polyaluminum while stirring, and continuously reacting for 1.5 hours after dropwise adding 1 part by weight of polyaluminum in 0.5 hour to obtain the cross-linked early-strength polycarboxylate water reducer of the embodiment.
Example 2
The embodiment provides a crosslinking type early strength polycarboxylate superplasticizer which is prepared from the following components: 100 parts of TPEG with the molecular weight of 4000, 5.8 parts of acrylic acid, 1.1 parts of maleic anhydride, 0.8 part of ammonium persulfate, 4 parts of sodium methallyl sulfonate, 0.3 part of VC and 0.5 part of polyethylenimine.
The cross-linking type early strength polycarboxylate superplasticizer is prepared by the following steps:
(1) adding 5.8 parts by weight of acrylic acid into 2 times of pure water by weight, and uniformly stirring to obtain a uniform solution A;
(2) adding 4 parts by weight of sodium methallyl sulfonate and 0.3 part by weight of VC into pure water with the weight being 20 times that of the sodium methallyl sulfonate, and uniformly stirring to obtain a uniform solution B;
(3) adding 100 parts by weight of TPEG into 0.78 times of pure water by weight, adding 1.1 part by weight of maleic anhydride, stirring until the TPEG is dissolved, adding 0.8 part by weight of ammonium persulfate at 15 ℃, and stirring for reacting for 8 min;
(4) dropwise adding the uniform solution A obtained in the step (1) and the uniform solution B obtained in the step (2) into the mixed solution obtained in the step (3) at a constant speed at the temperature of 20 ℃, and continuously reacting for 1.5 hours after dropwise adding is finished within 1.7 hours;
(5) and (3) adding water to dilute the mixed solution obtained in the step (4) until the mass concentration is 15%, dropwise adding polyethylenimine while stirring, and continuously reacting for 1.5 hours after 0.5 part by weight of polyethylenimine is completely dropwise added within 0.5 hour to obtain the cross-linked early-strength polycarboxylic acid water reducer of the embodiment.
Example 3
The embodiment provides a crosslinking type early strength polycarboxylate superplasticizer which is prepared from the following components: 100 parts of EPEG with the molecular weight of 5000, 10.2 parts of acrylic acid, 1.8 parts of maleic anhydride, 1.2 parts of sodium perborate, 5 parts of sodium methallyl sulfonate, 0.5 part of VC and 1.5 parts of carbodiimide.
The cross-linking type early strength polycarboxylate superplasticizer is prepared by the following steps:
(1) adding 10.2 parts by weight of acrylic acid into 2 times of pure water by weight, and uniformly stirring to obtain a uniform solution A;
(2) adding 5 parts by weight of sodium methallyl sulfonate and 0.5 part by weight of VC into pure water with the weight being 20 times that of the sodium methallyl sulfonate, and uniformly stirring to obtain a uniform solution B;
(3) adding 100 parts by weight of EPEG into 0.78 times of pure water by weight, adding 1.8 parts by weight of maleic anhydride, stirring until the mixture is dissolved, adding 1.2 parts by weight of sodium perborate at 25 ℃, and stirring for reaction for 10 min;
(4) dropwise adding the uniform solution A obtained in the step (1) and the uniform solution B obtained in the step (2) into the mixed solution obtained in the step (3) at a constant speed at 30 ℃, and continuously reacting for 1.5 hours after dropwise adding is finished within 2 hours;
(5) and (5) adding water to dilute the mixed solution obtained in the step (4) until the mass concentration is 20%, dropwise adding carbodiimide while stirring, and continuously reacting for 1.5 hours after dropwise adding 1.5 parts by weight of carbodiimide is completed within 0.5 hour to obtain the cross-linked early-strength polycarboxylate superplasticizer of the embodiment.
Example 4
The embodiment provides a crosslinking type early strength polycarboxylate superplasticizer which is prepared from the following components: 100 parts of EPEG with the molecular weight of 5000, 10.2 parts of acrylic acid, 1.8 parts of maleic anhydride, 1.6 parts of sodium perborate, 4 parts of sodium methallyl sulfonate, 0.6 part of VC and 1.2 parts of epoxy silane.
The cross-linking type early strength polycarboxylate superplasticizer is prepared by the following steps:
(1) adding 10.2 parts by weight of acrylic acid into 2 times of pure water by weight, and uniformly stirring to obtain a uniform solution A;
(2) adding 4 parts by weight of sodium methallyl sulfonate and 0.6 part by weight of VC into pure water with the weight being 20 times that of the sodium methallyl sulfonate, and uniformly stirring to obtain a uniform solution B;
(3) adding 100 parts by weight of EPEG into 0.78 times of pure water by weight, adding 1.8 parts by weight of maleic anhydride, stirring until the mixture is dissolved, adding 1.6 parts by weight of sodium perborate at 20 ℃, and stirring for reaction for 10 min;
(4) dropwise adding the uniform solution A obtained in the step (1) and the uniform solution B obtained in the step (2) into the mixed solution obtained in the step (3) at a constant speed at 35 ℃, and continuously reacting for 2 hours after dropwise adding is finished within 2 hours;
(5) and (3) adding water to dilute the mixed solution obtained in the step (4) to a mass concentration of 25%, dropwise adding epoxy silane while stirring, and continuously reacting for 1.5 hours after dropwise adding 1.2 parts by weight of epoxy silane is completed within 0.5 hour to obtain the cross-linking type early strength polycarboxylate water reducer of the embodiment.
Example 5
The embodiment provides a crosslinking type early strength polycarboxylate superplasticizer which is prepared from the following components: 100 parts of TPEG with the molecular weight of 4000, 8.5 parts of acrylic acid, 1.5 parts of maleic anhydride, 1.4 parts of hydrogen peroxide with the mass concentration of 27.5 percent, 4 parts of sodium methallyl sulfonate, 0.4 part of VC and 1.5 parts of epoxy silane.
The cross-linking type early strength polycarboxylate superplasticizer is prepared by the following steps:
(1) adding 8.5 parts by weight of acrylic acid into 2 times of pure water by weight, and uniformly stirring to obtain a uniform solution A;
(2) adding 4 parts by weight of sodium methallyl sulfonate and 0.4 part by weight of VC into pure water with the weight being 20 times that of the sodium methallyl sulfonate, and uniformly stirring to obtain a uniform solution B;
(3) adding 100 parts by weight of TPEG into 0.78 times of pure water by weight, adding 1.5 parts by weight of maleic anhydride, stirring until the TPEG is dissolved, adding 1.4 parts by weight of hydrogen peroxide with the mass concentration of 27.5% at 25 ℃, and stirring for reacting for 8 min;
(4) dropwise adding the uniform solution A obtained in the step (1) and the uniform solution B obtained in the step (2) into the mixed solution obtained in the step (3) at a constant speed at 30 ℃, and continuously reacting for 1.5h after dropwise adding is finished within 1.5 h;
(5) and (5) adding water to dilute the mixed solution obtained in the step (4) until the mass concentration is 20%, dropwise adding epoxy silane while stirring, and continuously reacting for 1.5 hours after dropwise adding 1.5 parts by weight of epoxy silane within 0.5 hour to obtain the cross-linking type early-strength polycarboxylate superplasticizer of the embodiment.
According to the JGT 223-plus-2017 polycarboxylate high-performance water reducer standard medium-early-strength water reducer detection test, the standard cement is selected, and other materials meet the standard requirements. The mixing proportion of the concrete is 360kg/m of cement3862kg/m of sand31013kg/m of stone3. The contrast water reducing agent comprises a commercially available 20% universal standard type polycarboxylic acid water reducing agent 1 and a commercially available 20% early strength type polycarboxylic acid water reducing agent 2. The test data are shown in Table 1.
Table 1 test data 1
The water reducing rate of the cross-linking type early strength polycarboxylate superplasticizer is similar to that of the existing polycarboxylate superplasticizer on the market, and reaches more than 28 percent; however, by adopting the crosslinking early-strength polycarboxylate superplasticizer provided by the invention, the concrete setting time is advanced by more than 1 hour, the 1-day compressive strength is obviously higher than that of the existing polycarboxylate superplasticizer, the later strength is not reduced, and the bleeding rate is obviously lower than that of the existing polycarboxylate superplasticizer.
Another concrete was used for the comparative test again: 450kg/m of mountain water PO42.5 cement3First-grade fly ash 45kg/m3692kg/m river sand35-20 continuous graded gravel 1237kg/m3135kg/m of drinking water3. The contrast water reducing agent is still 20 percent of the general standard type polycarboxylic acid water reducing agent 1 sold in the market and 20 percent of the early strength type polycarboxylic acid water reducing agent 2 sold in the market. The test data are shown in Table 2.
Table 2 test data 2
The slump loss of the crosslinking type early-strength polycarboxylate superplasticizer in 30 minutes is less than that of the existing polycarboxylate superplasticizer; by adopting the crosslinking early-strength polycarboxylate superplasticizer, the concrete setting time is advanced by more than 1 hour compared with the existing polycarboxylate superplasticizer, the 1-day compressive strength is obviously higher than that of the existing polycarboxylate superplasticizer, the later strength meets the trial-preparation requirement, and the concrete workability state is good.
Finally, it should be noted that: the above embodiments are only used to illustrate the technical solution of the present invention, and not to limit the same; while the invention has been described in detail and with reference to the foregoing embodiments, it will be understood by those skilled in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some or all of the technical features may be equivalently replaced; and the modifications or the substitutions do not make the essence of the corresponding technical solutions depart from the scope of the technical solutions of the embodiments of the present invention.
Moreover, those of skill in the art will appreciate that while some embodiments herein include some features included in other embodiments, not others, combinations of features of different embodiments are meant to be within the scope of the invention and form different embodiments. For example, in the claims above, any of the claimed embodiments may be used in any combination. The information disclosed in this background section is only for enhancement of understanding of the general background of the invention and should not be taken as an acknowledgement or any form of suggestion that this information forms the prior art already known to a person skilled in the art.
Claims (8)
1. A preparation method of a cross-linking type early-strength polycarboxylate superplasticizer is characterized by comprising the following steps:
102, adding a certain amount of unsaturated monocarboxylic acid monomer into a certain amount of pure water, and uniformly stirring to obtain a uniform solution A;
104, adding a certain amount of molecular weight regulator and a certain amount of reducing agent into a certain amount of pure water, and uniformly stirring to obtain a uniform solution B;
106, adding a certain amount of alkenyl polyoxyethylene ether into a certain amount of pure water, adding a certain amount of unsaturated dicarboxylic acid monomer, stirring until the unsaturated dicarboxylic acid monomer is dissolved, adding a certain amount of initiator at a certain temperature, and stirring for reacting for a period of time;
108, simultaneously dripping the uniform solution A and the uniform solution B into the mixed solution obtained in the step 106 at a certain temperature, and reacting for a certain time after finishing dripping;
step 110, adding water into the mixed solution obtained in the step 108 to dilute the mixed solution to a mass concentration of 15-25%, dropwise adding a carboxyl cross-linking agent at a constant speed while stirring, and reacting at normal temperature for 1.5h after dropwise adding is completed within 0.5h to obtain the cross-linked early-strength polycarboxylic acid water reducer;
wherein the mass ratio of the unsaturated monocarboxylic acid monomer, the unsaturated dicarboxylic acid monomer, the molecular weight regulator, the reducing agent, the initiator, the carboxyl cross-linking agent and the alkenyl polyoxyethylene ether is 5-10:1-2:2-5:0.2-0.6:0.6-1.6:0.5-1.5: 100; the molecular weight regulator is sodium methallyl sulfonate; the carboxyl cross-linking agent is one or two of polyaluminium, polyethylenimine, carbodiimide and epoxy silane; the molecular weight of the alkenyl polyoxyethylene ether is 3000-5000.
2. The method for preparing a cross-linking type early strength polycarboxylate water reducer according to claim 1, characterized in that the unsaturated monocarboxylic acid monomer is acrylic acid; the unsaturated dicarboxylic acid monomer is maleic anhydride.
3. The method for preparing the cross-linking type early strength polycarboxylate water reducer according to claim 1, wherein the reducing agent is vitamin C.
4. The preparation method of the cross-linking type early strength polycarboxylate superplasticizer according to claim 1, wherein the initiator is one or two of hydrogen peroxide, ammonium persulfate and sodium perborate.
5. A cross-linked early strength polycarboxylate water reducer prepared by the method of any one of claims 1 to 4.
6. The cross-linking type early strength polycarboxylate water reducer according to claim 5, characterized in that the cross-linking type early strength polycarboxylate water reducer is prepared from multiple components, wherein the components comprise alkenyl polyoxyethylene ether, unsaturated carboxylic acid monomer, molecular weight regulator, initiator, reducing agent and carboxyl cross-linking agent, and the mass ratio of the carboxyl cross-linking agent to the alkenyl polyoxyethylene ether is 0.5-1.5: 100.
7. The water reducer of claim 6, wherein the molecular weight of the alkenyl polyoxyethylene ether is 3000-5000.
8. Use of the cross-linked early strength polycarboxylate water reducer of any one of claims 5-7 in concrete.
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Denomination of invention: A cross-linked early strength carboxylic acid water reducer, its preparation method and application Effective date of registration: 20231129 Granted publication date: 20220708 Pledgee: Dezhou Rural Commercial Bank Co.,Ltd. Pledgor: Dezhou Zhongke New Material Co.,Ltd. Registration number: Y2023980068307 |