CN112341577A - Slump-retaining early-strength polycarboxylate superplasticizer and preparation method and application thereof - Google Patents
Slump-retaining early-strength polycarboxylate superplasticizer and preparation method and application thereof Download PDFInfo
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- 229920005646 polycarboxylate Polymers 0.000 title claims abstract description 50
- 239000008030 superplasticizer Substances 0.000 title claims abstract description 34
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 75
- 239000004567 concrete Substances 0.000 claims abstract description 32
- 239000011259 mixed solution Substances 0.000 claims description 72
- 239000003638 chemical reducing agent Substances 0.000 claims description 42
- 238000003756 stirring Methods 0.000 claims description 34
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 30
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 24
- 229920000570 polyether Polymers 0.000 claims description 24
- 239000003999 initiator Substances 0.000 claims description 19
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 18
- 238000002156 mixing Methods 0.000 claims description 18
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 17
- 239000000178 monomer Substances 0.000 claims description 17
- 239000002518 antifoaming agent Substances 0.000 claims description 16
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 14
- DZSVIVLGBJKQAP-UHFFFAOYSA-N 1-(2-methyl-5-propan-2-ylcyclohex-2-en-1-yl)propan-1-one Chemical compound CCC(=O)C1CC(C(C)C)CC=C1C DZSVIVLGBJKQAP-UHFFFAOYSA-N 0.000 claims description 13
- 239000002253 acid Substances 0.000 claims description 13
- 229920002818 (Hydroxyethyl)methacrylate Polymers 0.000 claims description 11
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 claims description 11
- 239000012986 chain transfer agent Substances 0.000 claims description 11
- DKIDEFUBRARXTE-UHFFFAOYSA-N 3-mercaptopropanoic acid Chemical compound OC(=O)CCS DKIDEFUBRARXTE-UHFFFAOYSA-N 0.000 claims description 10
- 230000002572 peristaltic effect Effects 0.000 claims description 10
- 239000007800 oxidant agent Substances 0.000 claims description 7
- 230000001590 oxidative effect Effects 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 6
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 6
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 6
- CWERGRDVMFNCDR-UHFFFAOYSA-N thioglycolic acid Chemical compound OC(=O)CS CWERGRDVMFNCDR-UHFFFAOYSA-N 0.000 claims description 6
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 5
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 claims description 4
- 239000003513 alkali Substances 0.000 claims description 4
- 238000005303 weighing Methods 0.000 claims description 4
- 230000009471 action Effects 0.000 claims description 3
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 3
- 229960005070 ascorbic acid Drugs 0.000 claims description 3
- 235000010323 ascorbic acid Nutrition 0.000 claims description 3
- 239000011668 ascorbic acid Substances 0.000 claims description 3
- 238000004090 dissolution Methods 0.000 claims description 3
- DNJIEGIFACGWOD-UHFFFAOYSA-N ethyl mercaptane Natural products CCS DNJIEGIFACGWOD-UHFFFAOYSA-N 0.000 claims description 3
- 229920002503 polyoxyethylene-polyoxypropylene Polymers 0.000 claims description 3
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 claims description 3
- 238000010526 radical polymerization reaction Methods 0.000 claims description 3
- DGVVWUTYPXICAM-UHFFFAOYSA-N β‐Mercaptoethanol Chemical compound OCCS DGVVWUTYPXICAM-UHFFFAOYSA-N 0.000 claims description 3
- SZHIIIPPJJXYRY-UHFFFAOYSA-M sodium;2-methylprop-2-ene-1-sulfonate Chemical compound [Na+].CC(=C)CS([O-])(=O)=O SZHIIIPPJJXYRY-UHFFFAOYSA-M 0.000 claims description 2
- 239000007787 solid Substances 0.000 claims description 2
- 230000001603 reducing effect Effects 0.000 abstract description 5
- 238000004519 manufacturing process Methods 0.000 abstract description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 abstract 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 abstract 1
- 238000009833 condensation Methods 0.000 abstract 1
- 230000005494 condensation Effects 0.000 abstract 1
- 239000011150 reinforced concrete Substances 0.000 abstract 1
- 239000004568 cement Substances 0.000 description 17
- 238000012360 testing method Methods 0.000 description 12
- 230000000694 effects Effects 0.000 description 7
- 238000000034 method Methods 0.000 description 7
- 230000006872 improvement Effects 0.000 description 5
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- XHZPRMZZQOIPDS-UHFFFAOYSA-N 2-Methyl-2-[(1-oxo-2-propenyl)amino]-1-propanesulfonic acid Chemical compound OS(=O)(=O)CC(C)(C)NC(=O)C=C XHZPRMZZQOIPDS-UHFFFAOYSA-N 0.000 description 3
- 238000007334 copolymerization reaction Methods 0.000 description 3
- 238000001723 curing Methods 0.000 description 3
- 239000008367 deionised water Substances 0.000 description 3
- 229910021641 deionized water Inorganic materials 0.000 description 3
- 230000000977 initiatory effect Effects 0.000 description 3
- 238000006116 polymerization reaction Methods 0.000 description 3
- 230000002265 prevention Effects 0.000 description 3
- 229920000536 2-Acrylamido-2-methylpropane sulfonic acid Polymers 0.000 description 2
- INRFMNKGJCROAZ-UHFFFAOYSA-N 2-hydroxy-2-sulfinylacetic acid Chemical compound OC(=O)C(O)=S=O INRFMNKGJCROAZ-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 125000003368 amide group Chemical group 0.000 description 2
- 238000010276 construction Methods 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 230000036571 hydration Effects 0.000 description 2
- 238000006703 hydration reaction Methods 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 230000037048 polymerization activity Effects 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000004576 sand Substances 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 239000004575 stone Substances 0.000 description 2
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- YHQXBTXEYZIYOV-UHFFFAOYSA-N 3-methylbut-1-ene Chemical compound CC(C)C=C YHQXBTXEYZIYOV-UHFFFAOYSA-N 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000004566 building material Substances 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- WCASXYBKJHWFMY-UHFFFAOYSA-N crotyl alcohol Chemical compound CC=CCO WCASXYBKJHWFMY-UHFFFAOYSA-N 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000007580 dry-mixing Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000009439 industrial construction Methods 0.000 description 1
- -1 isopentenyl Chemical group 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 125000005395 methacrylic acid group Chemical group 0.000 description 1
- 238000011415 microwave curing Methods 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- JRKICGRDRMAZLK-UHFFFAOYSA-L peroxydisulfate Chemical compound [O-]S(=O)(=O)OOS([O-])(=O)=O JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 description 1
- 229920000056 polyoxyethylene ether Polymers 0.000 description 1
- 229940051841 polyoxyethylene ether Drugs 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 230000002787 reinforcement Effects 0.000 description 1
- 230000008439 repair process Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000000979 retarding effect Effects 0.000 description 1
- 238000007790 scraping Methods 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- VQIDGTFLGAAJGI-UHFFFAOYSA-M sodium;prop-1-ene-1-sulfonate Chemical group [Na+].CC=CS([O-])(=O)=O VQIDGTFLGAAJGI-UHFFFAOYSA-M 0.000 description 1
- 238000005728 strengthening Methods 0.000 description 1
- 150000003871 sulfonates Chemical class 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
Images
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
- C04B24/16—Sulfur-containing compounds
- C04B24/161—Macromolecular compounds comprising sulfonate or sulfate groups
- C04B24/163—Macromolecular compounds comprising sulfonate or sulfate groups obtained by reactions only involving carbon-to-carbon unsaturated bonds
- C04B24/165—Macromolecular compounds comprising sulfonate or sulfate groups obtained by reactions only involving carbon-to-carbon unsaturated bonds 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
- 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
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Materials Engineering (AREA)
- Ceramic Engineering (AREA)
- Structural Engineering (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Curing Cements, Concrete, And Artificial Stone (AREA)
Abstract
The invention relates to a slump-retaining early-strength polycarboxylate superplasticizer, a preparation method and application thereof. The invention obviously improves the early strength of concrete, has outstanding slump retaining performance, good adaptability, does not influence the later strength, does not contain sulfate ions and chloride ions, and can be used for reinforced concrete and prefabricated parts. The slump-retaining early-strength polycarboxylate superplasticizer disclosed by the invention is high in water reducing rate, short in condensation time, simple and easily controllable in production process, most important, energy-saving, environment-friendly and pollution-free.
Description
Technical Field
The invention relates to the field of concrete admixtures, in particular to a slump loss resistant early strength type polycarboxylate superplasticizer and a preparation method and application thereof.
Background
In recent years, the construction scale of urban infrastructure in China is continuously enlarged, the real estate industry develops at a high speed, concrete which is one of the most common building materials is widely applied to a plurality of projects, and different types of projects have different requirements on various properties of the concrete. The development of industrial construction, prefabricated member production, rush repair and reinforcement engineering and the like has higher requirement on the early strength of concrete than that of common engineering, so that the development of early strength concrete is promoted.
The method for improving the early strength of concrete in the past practical engineering mainly comprises the following steps: the strength grade of the cement used in the mixed concrete is improved or the cement consumption is properly increased; the quality of the used aggregate is improved; and curing by adopting steam or microwave. The cement consumption is increased, the strength grade of the cement is improved, the construction cost is increased, resources are not saved, the cement cannot be generally adopted, the steam curing and the microwave curing are not only cost-improved but also environment-friendly, and a new technology needs to be developed to solve the problem of early strength concrete.
The polycarboxylate superplasticizer has the characteristics of low mixing amount, high water reducing rate, good workability of fresh concrete, low concrete shrinkage, environmental friendliness and the like, but the retarding effect of the common polycarboxylate superplasticizer can influence the hydration of cement, so that the early strength of concrete is slowly developed. At present, domestic and foreign researches on improving the early strength performance of the polycarboxylate superplasticizer mainly focus on the following two aspects: firstly, an early strength agent is added into a polycarboxylic acid water reducing agent, so that the water reducing agent has an early strength function, but if only a single early strength component is added, the performance of the water reducing agent has defects, so that various early strength components are often compounded (inorganic/inorganic, organic/inorganic), the early strength effect is outstanding, the defects of the single early strength component can be compensated, and the effects of making up for deficiencies and reducing the cost are achieved; secondly, synthesizing the early-strength polycarboxylate superplasticizer with early-strength performance by designing the molecular structure of the polycarboxylate superplasticizer. The method comprises the following steps: the structural parameters of the water reducer molecules are optimized by means of adjusting the length of the main side chain, the side chain density and the like of the polycarboxylic acid water reducer, and the early strength performance of the water reducer is improved; the second method comprises the following steps: grafting a monomer with an early strength function in the polycarboxylate superplasticizer molecule to synthesize the early strength polycarboxylate superplasticizer. Although the designed molecular structure can make the early strength effect better, the production cost is higher.
The patent 201610186337.5 discloses an ether early strength type polycarboxylate water reducer and a preparation method thereof, which comprises the steps of mixing and dissolving methylallyl alcohol polyoxyethylene ether with the molecular weight of 6000-plus 8000 and deionized water at normal temperature, adding a catalyst into the mixture, then sequentially dropwise adding a solution A formed by mixing acrylic acid, sulfonate unsaturated monomers and deionized water and a solution B formed by mixing an initiator, a chain transfer agent and deionized water for aqueous polymerization reaction, stirring after dropwise adding, and finally adding alkali liquor for neutralization to obtain the ether early strength type polycarboxylate water reducer. The main difference between this patent and the present invention is that it does not have slump retention.
Chinese patent CN102432776A reports a preparation method of an early-strength poly-carboxylic acid water reducing agent, which is obtained by copolymerizing four monomers, namely isopentene polyoxyalkylene ether, (methyl) acrylic acid, unsaturated double-bond sulfonate and acrylamide, in an aqueous solution by free radical initiation in the presence of a molecular weight regulator. Firstly, the polyether raw material used in the patent is limited to isopentenyl polyoxyalkylene ether, and in order to ensure that various monomers have good copolymerization efficiency in the polymerization process, the selection of an initiator and an initiation mode is limited to a persulfate initiator and a thermal initiation mode, so that the production process has low adjustability. Secondly, the unsaturated sulfonate preferably used in the patent is sodium propenyl sulfonate, the polymerization activity of the raw material is low, the chain transfer effect is obvious, the molecular weight of the prepared polycarboxylic acid water reducing agent is low, and the problems of insufficient slump retaining performance and unbalanced comprehensive performance are easy to occur in the practical application process. Finally, the amide groups used in the patent can accelerate cement hydration and realize early strengthening effect, but in alkaline cement slurry, the amide groups are gradually hydrolyzed to release ammonia gas, so that the environmental pollution is large.
Disclosure of Invention
In order to meet the requirements of the prior art, the slump loss resistance is good while the early strength of concrete is obviously improved, and the later strength of the concrete is not influenced, the invention provides the slump loss resistance early strength type polycarboxylate superplasticizer and the preparation method and the application thereof.
In order to solve the problems of the prior art, the invention adopts the technical scheme that:
a slump retaining early strength type polycarboxylate superplasticizer comprises the following components in parts by weight: 200 parts of polyether macromonomer, 5-15 parts of unsaturated acid, 0.5-2.5 parts of initiator (oxidant), 0.5-1 part of chain transfer agent, 0.1-0.5 part of reducing agent, 4-10 parts of unsaturated small monomer, 20-25 parts of hydroxyethyl methacrylate and 0.01-0.1 part of defoaming agent.
The improvement is that the polyether macromonomer is one or two of OXAB-501 and OXAC-608; the initiator (oxidant) is one or two of hydrogen peroxide, ammonium persulfate and potassium persulfate; the chain transfer agent is one or two of mercaptopropionic acid, mercaptoacetic acid and mercaptoethanol; the reducing agent is ascorbic acid (V)C) One or two of QM and 2-hydroxy-2-sulfinyl acetic acid; the unsaturated acid is one or two of Acrylic Acid (AA) and methacrylic acid; the unsaturated small monomer is one or two of 2-acrylamide-2-methylpropanesulfonic Acid (AMPS), sodium methallylsulfonate and acrylamide; the defoaming agent is one or two of polyoxyethylene Polyoxypropylene Pentaerythritol Ether (PPE), BK-J086 and HY-8090.
The improvement is a 5.5 molar ratio of acrylic acid to OXAC-608.
The improvement is that the molar ratio of OXAC-608 to 2-acrylamido-2-methylpropanesulfonic acid is 0.7.
The preparation method of the slump loss resistant early-strength polycarboxylate superplasticizer comprises the following specific steps:
step 1, monomer dissolution: weighing a metered polyether macromonomer, and completely dissolving the polyether macromonomer in water under the action of a magnetic stirrer to obtain a first mixed solution;
step 2, free radical polymerization: uniformly mixing a chain transfer agent, a reducing agent and water to obtain a mixed solution A; uniformly stirring unsaturated acid, unsaturated small monomer, hydroxyethyl methacrylate and water to obtain a mixed solution B;
step 3, adding an initiator, namely an oxidant, into the first mixed solution at the temperature of 40 +/-5 ℃, stirring for 10min, and then simultaneously dropwise adding the mixed solution A and the mixed solution B by using a peristaltic pump;
step 4, adding a defoaming agent after the dropwise addition is finished, and keeping the temperature for 1 h;
and 5, adjusting the pH to 6-7 by using alkali liquor sodium hydroxide to obtain the water reducer.
The improvement is that the mixed solution A is dropwise added for 3 hours and the mixed solution B is dropwise added for 3.5 hours in the step 3.
The application of the water reducer on concrete products requires water to dilute the water reducer until the solid content is 20-30%.
The polyether macromonomer OXAB-501 has the characteristics of narrow molecular weight distribution, low impurity content, high polymerization reaction activity and prominent slump retaining performance; OXAC-608 has the characteristics of high water reducing property and high early strength.
Has the advantages that:
compared with the prior art, the slump retaining early strength type polycarboxylate superplasticizer as well as the preparation method and the application thereof have the following advantages:
(1) the polyether macromonomer OXAB-501 used in the invention has the characteristics of stable quality, narrow molecular weight distribution, low impurity content, high polymerization activity and the like, and can be copolymerized with acrylic small monomers to generate a polycarboxylic acid water reducing agent with prominent slump retaining performance, so that the polyether macromonomer OXAB-501 has good adaptability and stability;
(2) the polyether macromonomer OXAC-608 used in the invention has the characteristics of high water reducing property and high early strength, and is compatible with acrylic acid for copolymerization to produce the polycarboxylate superplasticizer with early strength;
(3) 2-acrylamido-2-methylpropanesulfonic Acid (AMPS) has a sulfonic group with very strong polarity, has high copolymerization activity and also plays a role of a chain transfer agent, so that the viscosity and the average molecular weight of the water reducing agent are influenced;
(4) the synthesis process is simple and convenient, and easy to operate, and the prepared slump-retaining early-strength polycarboxylate water reducer has outstanding early strength performance and good slump-retaining performance, and the early strength performance of the slump-retaining early-strength polycarboxylate water reducer is obviously higher than that of a common polycarboxylate water reducer;
(5) the product has stable performance, can be stored for a long time, and is non-toxic and pollution-free;
(6) actual tests show that the slump loss resistant early-strength polycarboxylate superplasticizer prepared by the invention meets the index requirements of GB 8076-.
Drawings
FIG. 1 is an infrared spectrogram of the slump loss resistant early-strength polycarboxylate superplasticizer of the invention.
Detailed Description
The present invention will be further described with reference to specific examples.
A slump retaining early strength type polycarboxylate superplasticizer comprises the following components in parts by weight: 200 parts of polyether macromonomer, 5-15 parts of unsaturated acid, 0.5-2.5 parts of initiator (oxidant), 0.5-1 part of chain transfer agent, 0.1-0.5 part of reducing agent, 4-10 parts of unsaturated small monomer, 20-25 parts of hydroxyethyl methacrylate and 0.01-0.1 part of defoaming agent.
The improvement is that the polyether macromonomer is one or two of OXAB-501 and OXAC-608; the initiator (oxidant) is one or two of hydrogen peroxide, ammonium persulfate and potassium persulfate; the chain transfer agent is one or two of mercaptopropionic acid, mercaptoacetic acid and mercaptoethanol; the reducing agent is ascorbic acid (V)C) One or two of QM and 2-hydroxy-2-sulfinyl acetic acid; the unsaturated acid is one or two of Acrylic Acid (AA) and methacrylic acid; the unsaturated small monomer is 2-acrylamide-2-methylpropanesulfonic Acid (AMPS) or methacrylic sulfonic acidOne or two of sodium and acrylamide; the defoaming agent is one or two of polyoxyethylene Polyoxypropylene Pentaerythritol Ether (PPE), BK-J086 and HY-8090.
Wherein the molar ratio of acrylic acid to OXAC-608 is 5.5;
the molar ratio of OXAC-608 to 2-acrylamido-2-methylpropanesulfonic acid was 0.7.
The preparation method of the slump loss resistant early-strength polycarboxylate superplasticizer comprises the following specific steps:
step 1, monomer dissolution: weighing a metered polyether macromonomer, and completely dissolving the polyether macromonomer in water under the action of a magnetic stirrer to obtain a first mixed solution;
step 2, free radical polymerization: uniformly mixing a chain transfer agent, a reducing agent and water to obtain a mixed solution A; uniformly stirring unsaturated acid, unsaturated small monomer, hydroxyethyl methacrylate and water to obtain a mixed solution B;
step 3, adding an initiator, namely an oxidant, into the first mixed solution at the temperature of 40 +/-5 ℃, stirring for 10min, and then simultaneously dropwise adding the mixed solution A and the mixed solution B by using a peristaltic pump;
step 4, adding a defoaming agent after the dropwise addition is finished, and keeping the temperature for 1 h;
and 5, adjusting the pH to 6-7 by using alkali liquor sodium hydroxide to obtain the water reducer.
Wherein, the dropping time of the mixed solution A in the step 3 is 3 hours, and the dropping time of the mixed solution B is 3.5 hours.
Example 1
175g of polyether macromonomer (OXAB-501) and 100g of water are filled in a 500mL big beaker, and are heated and dissolved completely on a magnetic stirrer to obtain a first mixed solution;
mixing 0.85g mercaptopropionic acid and 0.35gVCPutting 48.5g of water into a 250mL beaker, and fully stirring on a magnetic stirrer to obtain a mixed solution A;
putting 24.7g of acrylic acid, 10.0g of AMPS, 22g of hydroxyethyl methacrylate and 26.5g of water into a 250mL beaker, and fully stirring on a magnetic stirrer to obtain a mixed solution B;
after the first mixed solution was completely dissolved, 1.75g of initiator H was added2O2And pouring the mixture into the mixer, stirring for 10min, simultaneously dropwise adding the mixed solution A, B into the mixed solution I by using a peristaltic pump, wherein the dropwise adding time is 3h and 3.5h respectively, after the dropwise adding is finished, adding 0.525g of defoaming agent, keeping the temperature for 1h, and adding sodium hydroxide to adjust the pH value to 6-7, thus obtaining the slump loss resistant early strength type polycarboxylate water reducer.
Example 2
175g of polyether macromonomer (OXAC-608) and 100g of water are filled in a 500mL big beaker, and are heated and dissolved completely on a magnetic stirrer to obtain a first mixed solution;
mixing 0.85g mercaptopropionic acid and 0.35gVCPutting 48.5g of water into a 250mL beaker, and fully stirring on a magnetic stirrer to obtain a mixed solution A;
putting 27.2g of acrylic acid, 0.7g of AMPS, 22g of hydroxyethyl methacrylate and 48.5g of water into a 250mL beaker, and fully stirring on a magnetic stirrer to obtain a mixed solution B;
and after the mixed solution I is completely dissolved, pouring 1.75g of initiator into the mixed solution I, stirring for 10min, simultaneously dropwise adding the mixed solution A, B into the mixed solution I by using a peristaltic pump, wherein the dropwise adding time is 3h and 3.5h respectively, after the dropwise adding is finished, adding 0.525g of defoaming agent, keeping the temperature for 1h, and adding sodium hydroxide to adjust the pH value to 6-7, thus obtaining the slump loss resistant early strength type polycarboxylate superplasticizer.
Example 3
175g of polyether macromonomer (OXAC-608) and 100g of water are filled in a 500mL big beaker, and are heated and dissolved completely on a magnetic stirrer to obtain a first mixed solution;
mixing 0.85g mercaptopropionic acid and 0.35gVCPutting 48.5g of water into a 250mL beaker, and fully stirring on a magnetic stirrer to obtain a mixed solution A;
placing 27.2g of acrylic acid, 4.3g of AMPS, 22g of hydroxyethyl methacrylate and 26.5g of water into a 250mL beaker, and fully stirring on a magnetic stirrer to obtain a mixed solution B;
and after the mixed solution I is completely dissolved, pouring 1.75g of initiator into the mixed solution I, stirring for 10min, simultaneously dropwise adding the mixed solution A, B into the mixed solution I by using a peristaltic pump, wherein the dropwise adding time is 3h and 3.5h respectively, after the dropwise adding is finished, adding 0.525g of defoaming agent, keeping the temperature for 1h, adding a proper amount of sodium hydroxide, and adjusting the pH value to 6-7 to obtain the slump loss prevention early strength type polycarboxylate superplasticizer.
Example 4
170g of polyether macromonomer (OXAC-608) and 100g of water are filled in a 500mL big beaker, and are heated and dissolved completely on a magnetic stirrer to obtain a first mixed solution;
mixing 0.85g mercaptopropionic acid and 0.75gVCPutting 48.5g of water into a 250mL beaker, and fully stirring on a magnetic stirrer to obtain a mixed solution A;
placing 27.2g of acrylic acid, 7.1g of AMPS and 26.5g of water into a 250mL beaker, and fully stirring on a magnetic stirrer to obtain a mixed solution B;
and after the mixed solution I is completely dissolved, pouring 1.75g of initiator into the mixed solution I, stirring for 10min, simultaneously dropwise adding the mixed solution A, B into the mixed solution I by using a peristaltic pump, wherein the dropwise adding time is 3h and 3.5h respectively, after the dropwise adding is finished, adding 0.35g of defoaming agent, keeping the temperature for 1h, and adding sodium hydroxide to adjust the pH value to 6-7, thus obtaining the slump loss resistant early strength type polycarboxylate superplasticizer.
Example 5
170g of polyether macromonomer (OXAB-501) and 100g of water are filled in a 500mL big beaker, and are heated and dissolved completely on a magnetic stirrer to obtain a first mixed solution;
mixing 0.85g mercaptopropionic acid and 0.35gVCPutting 48.5g of water into a 250mL beaker, and fully stirring on a magnetic stirrer to obtain a mixed solution A;
putting 27.2g of acrylic acid, 10.0g of AMPS, 22g of hydroxyethyl methacrylate and 26.5g of water into a 250mL beaker, and fully stirring on a magnetic stirrer to obtain a mixed solution B;
and after the mixed solution I is completely dissolved, pouring 1.4g of initiator into the mixed solution I, stirring for 10min, simultaneously dropwise adding the mixed solution A, B into the mixed solution I by using a peristaltic pump, wherein the dropwise adding time is 3h and 3.5h respectively, after the dropwise adding is finished, adding 0.35g of defoaming agent, keeping the temperature for 1h, and adding a proper amount of sodium hydroxide to adjust the pH value to 6-7, thus obtaining the slump loss prevention early strength type polycarboxylate superplasticizer.
Example 6
175g of polyether macromonomer (OXAC-608) and 100g of water are filled in a 500mL big beaker, and are heated and dissolved completely on a magnetic stirrer to obtain a first mixed solution;
mixing 1.105g mercaptopropionic acid, 0.7gVCPutting 44.2g of water into a 250mL beaker, and fully stirring on a magnetic stirrer to obtain a mixed solution A;
putting 24.7g of acrylic acid, 12.8g of AMPS and 44.5g of water into a 250mL beaker, and fully stirring on a magnetic stirrer to obtain a mixed solution B;
and after the mixed solution I is completely dissolved, pouring 1.4g of initiator into the mixed solution I, stirring for 10min, simultaneously dropwise adding the mixed solution A, B into the mixed solution I by using a peristaltic pump, wherein the dropwise adding time is 3h and 3.5h respectively, after the dropwise adding is finished, adding 0.525 of defoaming agent, keeping the temperature for 1h, adding a proper amount of sodium hydroxide, and adjusting the pH value to 6-7 to obtain the slump-retaining early strength type polycarboxylate superplasticizer.
Example 7
Adding 165g of polyether macromonomer (OXAC-608) and 100g of water into a 500mL big beaker, and heating and completely dissolving on a magnetic stirrer to obtain a first mixed solution;
mixing 0.85g mercaptopropionic acid and 0.35gVCPutting 48.5g of water into a 250mL beaker, and fully stirring on a magnetic stirrer to obtain a mixed solution A;
putting 27.2g of acrylic acid, 2.1g of AMPS, 22g of hydroxyethyl methacrylate and 26.5g of water into a 250mL beaker, and fully stirring on a magnetic stirrer to obtain a mixed solution B;
and after the mixed solution I is completely dissolved, pouring 1.75g of initiator into the mixed solution I, stirring for 10min, simultaneously dropwise adding the mixed solution A, B into the mixed solution I by using a peristaltic pump, wherein the dropwise adding time is 3h and 3.5h respectively, after the dropwise adding is finished, adding 0.35g of defoaming agent, keeping the temperature for 1h, adding a proper amount of sodium hydroxide, and adjusting the pH value to 6-7 to obtain the slump-retaining early strength type polycarboxylate superplasticizer.
The application method of the slump-retaining early-strength polycarboxylate superplasticizer comprises the following steps:
the concrete test block without the slump loss resistant early strength type polycarboxylate water reducer and the 21 concrete test blocks using the slump loss resistant early strength type polycarboxylate water reducer of the 7 embodiments are subjected to cement paste fluidity test according to the standard of GB/T8077-.
The cement paste fluidity test method comprises the following steps: weighing 300g of cement, pouring the cement into a cement paste stirring pot, adding a self-made slump retaining early strength type polycarboxylate superplasticizer with the mixing amount of 1.2% and 87g or 105g of water, immediately stirring (slow speed 120s, stop 15s and fast speed 120s), quickly injecting the mixed paste into a truncated cone circular mold, leveling by a scraper, vertically lifting the truncated cone circular mold upwards, simultaneously starting timing for 30s, allowing the cement paste to flow on a glass plate, measuring the maximum diameter of two mutually vertical directions of a flowing part by a ruler after 30s, and taking the average value as the fluidity of the cement paste.
Concrete mix ratio table 1:
the concrete test block without the slump loss resistant early strength type polycarboxylate water reducer and the 21 concrete test blocks using the slump loss resistant early strength type polycarboxylate water reducer of the 7 embodiments are subjected to slump test according to the standard of GB/T50080-2016 ordinary concrete mixture performance test method.
Slump test method: putting cement, sand and stones into a single horizontal shaft type forced mixer with the nominal capacity of 60L at one time, performing dry mixing uniformly, adding mixing water mixed with a liquid additive, stirring for 2min, discharging, manually turning and mixing uniformly on an iron plate, wetting a slump cone and a bottom plate, placing the cone in the center of the bottom plate, uniformly filling the mixed concrete sample into the cone in three layers by using a small shovel, tamping the concrete sample by using a tamping bar, inserting and tamping the top layer, scraping redundant concrete, leveling by using a trowel, vertically and stably lifting the slump cone within 5-10s, and measuring the height difference between the height of the cone and the highest point of the slump concrete sample, namely the slump value.
The concrete test block without the slump loss resistant early strength type polycarboxylate water reducer and the 21 concrete test blocks using the slump loss resistant early strength type polycarboxylate water reducer of the 7 embodiments are measured according to the standard of GB 8076-.
And (3) determination of the compressive strength ratio: putting cement, sand and stone into a single horizontal shaft type forced stirrer with the nominal capacity of 60L at one time, uniformly dry-stirring, adding mixing water doped with a liquid additive, stirring for 2min, discharging, manually stirring uniformly on an iron plate, putting into a 100 x 100 mould, respectively curing for 1d, 3d, 7d and 28d, measuring the compressive strength under a press machine, and calculating to obtain the compressive strength ratio.
The test results of the concrete test block without the slump loss resistant early strength polycarboxylate water reducer and the 21 concrete test blocks using the slump loss resistant early strength polycarboxylate water reducers of the 7 examples are shown in the second table.
Table 2 slump loss prevention early strength type polycarboxylate superplasticizer performance detection data
From the experimental detection data, the strength of the concrete is improved by 10-30% for 1d, 4-18% for 3d, 20-40% for 7d and 10-20% for 28d, which are far higher than the standard requirement of GB8076-2008 concrete admixture.
The above description is only a preferred embodiment of the present invention, and it will be apparent to those skilled in the art that various modifications and variations can be made without departing from the technical principles of the present invention, and these modifications and variations should also be construed as the scope of the present invention.
Claims (7)
1. The slump loss resistant early-strength polycarboxylate superplasticizer is characterized by comprising the following components in parts by weight: 200 parts of polyether macromonomer, 5-15 parts of unsaturated acid, 0.5-2.5 parts of initiator, 0.5-1 part of chain transfer agent, 0.1-0.5 part of reducing agent, 4-10 parts of unsaturated small monomer, 20-25 parts of hydroxyethyl methacrylate and 0.01-0.1 part of defoaming agent.
2. The slump retaining early-strength polycarboxylate superplasticizer according to claim 1, wherein the polyether macromonomer is one or two of OXAB-501 and OXAC-608; the initiator is one or two of hydrogen peroxide, ammonium persulfate and potassium persulfate; the chain transfer agent is one or two of mercaptopropionic acid, mercaptoacetic acid and mercaptoethanol; the reducing agent is one or two of ascorbic acid, QM and 2-hydroxy-2-sulfinic acid; the unsaturated acid is one or two of acrylic acid and methacrylic acid; the unsaturated small monomer is one or two of 2-acrylamide-2-methylpropanesulfonic acid, sodium methallylsulfonate and acrylamide; the defoaming agent is one or two of polyoxyethylene polyoxypropylene pentaerythritol ether, BK-J086 and HY-8090.
3. The slump retaining and early strength type polycarboxylate water reducer as claimed in claim 2, wherein the molar ratio of acrylic acid to OXAC-608 is 5.5.
4. The slump retaining and early strength type polycarboxylate water reducer as claimed in claim 2, wherein the molar ratio of OXAC-608 to 2-acrylamide-2-methylpropanesulfonic acid is 0.7.
5. The preparation method of the slump-retaining early-strength polycarboxylate superplasticizer according to claim 1 is characterized by comprising the following steps of:
step 1, monomer dissolution: weighing a metered polyether macromonomer, and completely dissolving the polyether macromonomer in water under the action of a magnetic stirrer to obtain a first mixed solution;
step 2, free radical polymerization: uniformly mixing a chain transfer agent, a reducing agent and water to obtain a mixed solution A; uniformly stirring unsaturated acid, unsaturated small monomer, hydroxyethyl methacrylate and water to obtain a mixed solution B;
step 3, adding an initiator, namely an oxidant, into the first mixed solution at the temperature of 40 +/-5 ℃, stirring for 10min, and then simultaneously dropwise adding the mixed solution A and the mixed solution B by using a peristaltic pump;
step 4, adding a defoaming agent after the dropwise addition is finished, and keeping the temperature for 1 h;
and 5, adjusting the pH to 6-7 by using alkali liquor sodium hydroxide to obtain the water reducer.
6. The preparation method of the slump loss resistant early-strength polycarboxylate superplasticizer according to claim 5, wherein in the step 3, the dropping time of the mixed solution A is 3 hours, and the dropping time of the mixed solution B is 3.5 hours.
7. The use of a water reducer as claimed in claim 1 or claim 5 in concrete products, wherein the water reducer is diluted with water to a solids content of 20-30%.
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