CN110396158B - Marine concrete shrinkage-reducing water reducing agent and application method thereof - Google Patents
Marine concrete shrinkage-reducing water reducing agent and application method thereof Download PDFInfo
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- CN110396158B CN110396158B CN201910741085.1A CN201910741085A CN110396158B CN 110396158 B CN110396158 B CN 110396158B CN 201910741085 A CN201910741085 A CN 201910741085A CN 110396158 B CN110396158 B CN 110396158B
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 103
- 239000004567 concrete Substances 0.000 title claims abstract description 81
- 239000003638 chemical reducing agent Substances 0.000 title claims abstract description 55
- 238000000034 method Methods 0.000 title claims abstract description 21
- 239000000203 mixture Substances 0.000 claims abstract description 41
- 239000000178 monomer Substances 0.000 claims abstract description 35
- 239000000243 solution Substances 0.000 claims abstract description 31
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 claims abstract description 30
- 239000004721 Polyphenylene oxide Substances 0.000 claims abstract description 19
- 239000007864 aqueous solution Substances 0.000 claims abstract description 19
- 229920000570 polyether Polymers 0.000 claims abstract description 19
- 229960005070 ascorbic acid Drugs 0.000 claims abstract description 15
- 235000010323 ascorbic acid Nutrition 0.000 claims abstract description 15
- 239000011668 ascorbic acid Substances 0.000 claims abstract description 15
- 238000002156 mixing Methods 0.000 claims abstract description 12
- 238000003756 stirring Methods 0.000 claims abstract description 12
- 239000012986 chain transfer agent Substances 0.000 claims abstract description 9
- 150000002978 peroxides Chemical class 0.000 claims abstract description 7
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims abstract description 6
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims abstract description 5
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims abstract description 5
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 claims abstract description 5
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 claims abstract description 5
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims abstract description 5
- FQPSGWSUVKBHSU-UHFFFAOYSA-N methacrylamide Chemical compound CC(=C)C(N)=O FQPSGWSUVKBHSU-UHFFFAOYSA-N 0.000 claims abstract description 5
- 230000007935 neutral effect Effects 0.000 claims abstract description 5
- 229920000056 polyoxyethylene ether Polymers 0.000 claims abstract description 5
- 229940051841 polyoxyethylene ether Drugs 0.000 claims abstract description 5
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 claims abstract description 4
- QZPSOSOOLFHYRR-UHFFFAOYSA-N 3-hydroxypropyl prop-2-enoate Chemical compound OCCCOC(=O)C=C QZPSOSOOLFHYRR-UHFFFAOYSA-N 0.000 claims abstract description 4
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 4
- 238000001816 cooling Methods 0.000 claims abstract description 3
- 238000009413 insulation Methods 0.000 claims abstract description 3
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 36
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims description 36
- 229910000030 sodium bicarbonate Inorganic materials 0.000 claims description 18
- 235000017557 sodium bicarbonate Nutrition 0.000 claims description 18
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 18
- BNIILDVGGAEEIG-UHFFFAOYSA-L disodium hydrogen phosphate Chemical compound [Na+].[Na+].OP([O-])([O-])=O BNIILDVGGAEEIG-UHFFFAOYSA-L 0.000 claims description 14
- 239000001488 sodium phosphate Substances 0.000 claims description 14
- CWERGRDVMFNCDR-UHFFFAOYSA-N thioglycolic acid Chemical compound OC(=O)CS CWERGRDVMFNCDR-UHFFFAOYSA-N 0.000 claims description 14
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 claims description 14
- 229910000406 trisodium phosphate Inorganic materials 0.000 claims description 14
- 235000019801 trisodium phosphate Nutrition 0.000 claims description 14
- 239000000463 material Substances 0.000 claims description 13
- DKIDEFUBRARXTE-UHFFFAOYSA-N 3-mercaptopropanoic acid Chemical compound OC(=O)CCS DKIDEFUBRARXTE-UHFFFAOYSA-N 0.000 claims description 5
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium peroxydisulfate Substances [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 5
- VAZSKTXWXKYQJF-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)OOS([O-])=O VAZSKTXWXKYQJF-UHFFFAOYSA-N 0.000 claims description 5
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 5
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 4
- 239000003795 chemical substances by application Substances 0.000 claims description 4
- JHUFGBSGINLPOW-UHFFFAOYSA-N 3-chloro-4-(trifluoromethoxy)benzoyl cyanide Chemical compound FC(F)(F)OC1=CC=C(C(=O)C#N)C=C1Cl JHUFGBSGINLPOW-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 3
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 claims description 2
- 238000005260 corrosion Methods 0.000 abstract description 8
- 230000007797 corrosion Effects 0.000 abstract description 8
- 238000002360 preparation method Methods 0.000 abstract description 5
- 239000013535 sea water Substances 0.000 abstract description 4
- 229920000642 polymer Polymers 0.000 abstract 1
- 238000006243 chemical reaction Methods 0.000 description 18
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- 239000000376 reactant Substances 0.000 description 8
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 7
- 230000003628 erosive effect Effects 0.000 description 7
- 239000011259 mixed solution Substances 0.000 description 7
- 239000011575 calcium Substances 0.000 description 5
- 239000000835 fiber Substances 0.000 description 4
- 239000004568 cement Substances 0.000 description 3
- 238000011056 performance test Methods 0.000 description 3
- 238000004321 preservation Methods 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- LEAHFJQFYSDGGP-UHFFFAOYSA-K trisodium;dihydrogen phosphate;hydrogen phosphate Chemical compound [Na+].[Na+].[Na+].OP(O)([O-])=O.OP([O-])([O-])=O LEAHFJQFYSDGGP-UHFFFAOYSA-K 0.000 description 3
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 238000010276 construction Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 229910001653 ettringite Inorganic materials 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 239000004566 building material Substances 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 239000001506 calcium phosphate Substances 0.000 description 1
- 229910000389 calcium phosphate Inorganic materials 0.000 description 1
- 235000011010 calcium phosphates Nutrition 0.000 description 1
- 238000003763 carbonization Methods 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 230000007123 defense Effects 0.000 description 1
- 230000003111 delayed effect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 239000010881 fly ash Substances 0.000 description 1
- 239000004574 high-performance concrete Substances 0.000 description 1
- 239000011372 high-strength concrete Substances 0.000 description 1
- 238000006703 hydration reaction Methods 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 244000005700 microbiome Species 0.000 description 1
- 235000010755 mineral Nutrition 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 229920005646 polycarboxylate Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000004904 shortening Methods 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000002893 slag Substances 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000008961 swelling Effects 0.000 description 1
- QORWJWZARLRLPR-UHFFFAOYSA-H tricalcium bis(phosphate) Chemical compound [Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O QORWJWZARLRLPR-UHFFFAOYSA-H 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B40/00—Processes, in general, for influencing or modifying the properties of mortars, concrete or artificial stone compositions, e.g. their setting or hardening ability
- C04B40/0028—Aspects relating to the mixing step of the mortar preparation
- C04B40/0039—Premixtures of ingredients
-
- 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
-
- 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
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Engineering & Computer Science (AREA)
- Ceramic Engineering (AREA)
- Materials Engineering (AREA)
- Structural Engineering (AREA)
- Curing Cements, Concrete, And Artificial Stone (AREA)
Abstract
The invention relates to a marine concrete shrinkage-reducing water reducing agent and an application method thereof, belonging to the field of concrete water reducing agents. The preparation method of the water reducing agent comprises the following steps: adding the monomer A into water, stirring and dissolving, then adding peroxide, stirring uniformly, then respectively adding a mixed aqueous solution of ascorbic acid and a chain transfer agent and a monomer B aqueous solution, carrying out thermal insulation polymerization for 1-1.5h, then cooling to 30-35 ℃, and finally adding an anti-erosion component to adjust the pH value of the solution to be neutral, thus obtaining the anti-erosion polymer. Wherein the monomer A is one or a mixture of modified polyether TPEG or allyl polyoxyethylene ether HPEG, and the monomer B is one or a mixture of acrylic acid, hydroxyethyl acrylate, hydroxypropyl acrylate, acrylamide, methacrylic acid, methyl methacrylate or methacrylamide. The water reducer has the advantages of less mixing amount of anti-erosion components and simple preparation method, and the prepared concrete can effectively reduce the corrosion of sulfate radicals in seawater on the basis of water reduction, shrinkage reduction and the like, and has good market application prospect.
Description
Technical Field
The invention relates to a marine concrete shrinkage-reducing water reducer, and belongs to the field of concrete water reducers.
The invention also relates to an application method of the marine concrete shrinkage-reducing water reducing agent.
Background
Concrete is the most widely used and most used civil engineering material in the world today. The characteristics of the concrete structure material and the using environment cause the problems of insufficient durability and the like of the concrete structure, which causes great economic loss to the country, and the problems of resource, energy and environmental protection caused by the problem are more and more prominent. The current engineering world generally focuses on the problem of durability of a concrete structure, and the method not only relates to the control of maintenance and reconstruction cost of the concrete structure, but also is closely related to energy conservation and emission reduction, environmental protection and sustainable development of the society.
The shrinkage of concrete is a phenomenon that the volume of concrete is reduced after the concrete is poured and hardened, if the shrinkage stress generated by excessive shrinkage causes the concrete to crack, the structural strength is reduced, the crack also provides a channel for air and water to enter the concrete, so that the concrete is easy to generate carbonization corrosion, and the steel bar corrosion also causes freeze-thaw cycle in cold areas, thereby greatly reducing the durability of the concrete and shortening the service life of buildings. In addition, High Performance Concrete (HPC) and High Strength Concrete (HSCPI) which are developed vigorously in recent years are characterized by small water consumption, large cement consumption and addition of fine reactive admixtures, so that early-stage cementing materials are quickly hydrated to cause the rapid consumption of free water in the concrete, and self-drying is generated to cause the reduction and shrinkage of macroscopic volume of the concrete while the internal structure is dense, thereby further increasing the stress in the concrete and aggravating the cracking tendency of the concrete.
In order to solve the problems, methods such as adding an expanding agent and adding fibers are used in the market, but the use of the expanding agent particularly requires that concrete is cured with water in the early stage, the conditions are harsh, the concrete has serious cement adaptability and the generation of ettringite is delayed, and the like. The added fiber can only improve the crack resistance of concrete, does not reduce the shrinkage of concrete, has high fiber price and has the problem of compatibility with the concrete, and greatly limits the popularization of the fiber. Scientists focused on finding a better method, and in the eighties of the last century, concrete shrinkage reducers appeared, which reduce the surface tension of water from the microstructure in concrete capillary pores and reduce the shrinkage force in the water evaporation process, thereby reducing the shrinkage of concrete and achieving the purpose of reducing concrete cracks.
The patent CN102765899A of Shandonghua Wei silver Kai building materials science and technology Limited company discloses a low-air-entraining shrinkage-reducing polycarboxylate water reducer prepared by copolymerizing a monomer A and a monomer B according to the molar ratio of 1:3-3.5, wherein the monomer A is modified polyether TPEG; the monomer B is one or more of acrylic acid, methyl acrylate, acrylamide, methacrylic acid, methyl methacrylate and methacrylamide. The preparation method comprises the following steps: firstly adding H into the modified polyether TPEG aqueous solution at the temperature of 50-55 DEG C2O2Stirring for 10-15min, simultaneously dropwise adding the ascorbic acid, the chain transfer agent mixed aqueous solution and the monomer B solution respectively, continuously reacting for 0.5-1.0h under heat preservation after dropwise adding, and adjusting the pH value to obtain the water reducer. The water reducing agent not only has higher water reducing rate, but also has lower air content and certain reduction function when being used for concrete, and is a multifunctional high-efficiency water reducing agent with strong adaptability which integrates water reducing, reduction and low air entraining.
China is a big ocean country, ocean reef island engineering construction faces heavy tasks in recent years, and foundation facilities such as civil and military wharfs, offshore airports, offshore wind power stations, offshore lighthouses and radar stations, reef edge defense works and the like need a large amount of reef island high-performance ocean concrete for construction. In the marine environment, general concrete can be corroded by sulfate ions, chloride ions, microorganisms and the like, so the key problem of the island reef high-performance marine concrete is how to reduce various corrosion from seawater, particularly the corrosion of the sulfate ions which are greatly influenced. At present, slag and fly ash are directly doped in the market, so that the effect of resisting sulfuric acid corrosion can be better achieved, certain side effect can be achieved on the structure, and the doping amount is large. There is no study on the addition of an anti-erosion component to an admixture such as a water reducing agent with a small addition amount.
In view of the above, the present invention is particularly proposed.
Disclosure of Invention
The invention aims to provide a marine concrete shrinkage-reducing water reducing agent which is used as a concrete additive, the raw materials are cheap and easy to obtain, the mixing amount of anti-erosion components is small, the preparation method is simple, the prepared concrete can effectively reduce the corrosion of sulfate radicals in seawater on the basis of water reduction, shrinkage reduction and the like, and the marine concrete shrinkage-reducing water reducing agent has good market application prospect.
In order to achieve the purpose, the invention provides the following technical scheme:
a marine concrete reduction type water reducing agent comprises the following steps:
(1) adding the monomer A into water, stirring and dissolving;
(2) adding peroxide into the solution obtained in the step (1), and uniformly stirring; the stirring time is preferably 10-15 min.
(3) Respectively adding a mixed aqueous solution of ascorbic acid and a chain transfer agent and a monomer B aqueous solution into the solution obtained in the step (2), carrying out thermal insulation polymerization for 1-1.5h, and then cooling to 30-35 ℃;
(4) adding an anti-erosion component to adjust the pH value of the solution to be neutral, thus obtaining the anti-erosion agent;
the monomer A is one or a mixture of modified polyether TPEG or allyl polyoxyethylene ether HPEG, and the monomer B is one or a mixture of acrylic acid, hydroxyethyl acrylate, hydroxypropyl acrylate, acrylamide, methacrylic acid, methyl methacrylate or methacrylamide.
The molar ratio of the monomer A to the monomer B is 1: 2-5.5.
The molecular weight of the monomer A is between 2000 and 2500. Preferably, the average molecular weight of the monomer a is 2400.
The peroxide is one or a mixture of hydrogen peroxide or ammonium persulfate; the mass ratio of the peroxide to the monomer A is 0.1-0.15: 1.
The mass ratio of the using amount of the ascorbic acid to the monomer A is 0.02-0.05: 1.
The chain transfer agent is one or a mixture of sodium allylsulfonate, sodium methallylsulfonate, thioglycolic acid or mercaptopropionic acid; the mass ratio of the using amount of the chain transfer agent to the monomer A is 0.05-0.2: 1.
The dripping time of the ascorbic acid and the chain transfer agent is about 3.0-3.5 h; the dripping time of the monomer B is 2.5-3.0 h.
The anti-erosion component is a mixture of sodium carbonate and sodium bicarbonate or a mixture of trisodium phosphate and disodium hydrogen phosphate.
The corrosion of the concrete by sulfate in seawater is greatly related to the mineral composition in the cement clinker, particularly Ca (OH) formed after hydration2Can participate and drive the sulfate erosion reaction. Therefore, the addition of sodium carbonate in the present invention can be combined with Ca (OH)2Reacting to form sodium hydroxide and insoluble calcium carbonate, and adding trisodium phosphate to react with Ca (OH)2The reaction produces sodium hydroxide and insoluble calcium phosphate. Thereby preventing Ca (OH)2And the reaction with sulfate reduces the occurrence of sulfate erosion reaction. And the sodium bicarbonate is added while the sodium carbonate is added, so that the water reducing agent is adjusted to be neutral, the reaction of the sodium carbonate and the water is inhibited through chemical kinetics, and the same principle is also realized by adding the disodium hydrogen phosphate.
In the mixture of sodium carbonate and sodium bicarbonate, the molar ratio of the sodium carbonate to the sodium bicarbonate is 5-10: 1; in the mixture of the trisodium phosphate and the disodium hydrogen phosphate, the molar ratio of the trisodium phosphate to the disodium hydrogen phosphate is 8-10: 1. When the amount of the mixture of sodium carbonate and sodium bicarbonate or the mixture of trisodium phosphate and disodium hydrogen phosphate is too large, the mixture can cause the ettringite to be separated in a gel-like manner, and bring about harmful swelling.
The mass ratio of the dosage of the anti-erosion component to the monomer A is 0.1-0.15: 1.
In the step (1), the temperature is controlled to be 13-25 ℃ in the stirring and dissolving process, and the concentration of the monomer A is controlled to be 56-70%.
An application method of the marine concrete reduction type water reducing agent comprises the following steps: the mixing amount of the water reducing agent in the concrete is 0.6-1.0% of the weight of the cementing material.
Compared with the prior art, the invention adds a very small amount of anti-erosion component, on one hand, the polymerization product tends to be neutral in the preparation process of the water reducing agentOn the other hand, the composition can effectively prevent Ca (OH)2Participates and drives the sulfate erosion reaction, the erosion resistance coefficient of the prepared concrete can reach 0.95 at most, and the concrete has good market application prospect.
Detailed Description
The technical solution of the present invention is further described in detail by the following examples, which are only for explaining the present invention and are not to be construed as limiting the present invention.
Example 1
A marine concrete reduction type water reducing agent comprises the following steps:
(1) 360 parts by mass (0.15mol) of modified polyether TPEG with the average molecular weight of 2400 and 280 parts by mass of water are mixed in a reactor, and the mixture is stirred at the temperature of 20 ℃ until the mixture is completely dissolved, wherein the concentration of the modified polyether TPEG is 56%.
(2) Adding 36 parts by mass of H to the solution obtained in the step (1)2O2The reaction was stirred for 10 min.
(3) Respectively adding 10.8 parts by mass of a mixed aqueous solution of ascorbic acid and 18 parts by mass of mercaptopropionic acid (wherein the mass of water is 54 parts) into the solution obtained in the step (2), and dropwise adding for 3 hours; then, 21 parts by mass (0.3mol) of an acrylic acid aqueous solution (80 parts by mass of water) was added thereto, and the dropping time was 2.5 hours, followed by continued reaction at 40 ℃ for 1 hour with heat preservation. Then 150 parts by mass of water was added thereto, and the temperature was reduced to 30 ℃.
(4) And (3) adding 36 parts by mass of a mixed solution of sodium carbonate and sodium bicarbonate (wherein the molar ratio of the sodium carbonate to the sodium bicarbonate is 5:1) into the reactant obtained in the step (3) to adjust the pH value to about 7, thus obtaining the sodium bicarbonate.
The application method of the marine concrete shrinkage-reducing water reducer comprises the following steps: the mixing amount of the water reducing agent in the concrete is 1 percent of the weight of the cementing material.
Example 2
A marine concrete reduction type water reducing agent comprises the following steps:
(1) 240 parts by mass (0.1mol) of allyl polyoxyethylene ether HPEG with the average molecular weight of 2400 and 103 parts by mass of water are mixed in a reactor, and the mixture is stirred at the temperature of 13 ℃ until the mixture is completely dissolved, wherein the concentration of the allyl polyoxyethylene ether HPEG is 70%.
(2) Adding 36 parts by mass of H to the solution obtained in the step (1)2O2The reaction was stirred for 15 min.
(3) Respectively adding 4.8 parts by mass of a mixed aqueous solution of ascorbic acid and 24 parts by mass of thioglycolic acid (42 parts by mass of water) into the solution obtained in the step (2), wherein the dropwise adding time is 3.5 hours; then, 62 parts by mass (0.55mol) of an aqueous solution of hydroxyethyl acrylate (wherein the amount of water is 102 parts by mass) was added thereto, the dropping time was 3 hours, and the reaction was continued for 1 hour at 40 ℃. Then 150 parts by mass of water was added thereto, and the temperature was reduced to 30 ℃.
(4) And (3) adding 36 parts by mass of a mixed solution of sodium carbonate and sodium bicarbonate (wherein the molar ratio of the sodium carbonate to the sodium bicarbonate is 10:1) into the reactant obtained in the step (3) to adjust the pH value to about 7, thus obtaining the sodium bicarbonate.
The application method of the marine concrete shrinkage-reducing water reducer comprises the following steps: the mixing amount of the water reducing agent in the concrete is 0.6 percent of the weight of the cementing material.
Example 3
A marine concrete reduction type water reducing agent comprises the following steps:
(1) 200 parts by mass (0.1mol) of modified polyether TPEG with the average molecular weight of 2000 and 103 parts by mass of water are mixed in a reactor, and the mixture is stirred at the temperature of 25 ℃ until the mixture is completely dissolved, wherein the concentration of the modified polyether TPEG is 66%.
(2) And (2) adding 24 parts by mass of ammonium persulfate into the solution obtained in the step (1), and stirring for reacting for 15 min.
(3) Respectively adding 10 parts by mass of ascorbic acid and 40 parts by mass of a mixed aqueous solution of sodium methallyl sulfonate (wherein the mass of water is 64 parts), and the dropwise adding time is 3.2 h; then, 45.7 parts by mass (0.35mol) of an aqueous solution of hydroxypropyl acrylate (80 parts by mass of water) was added thereto, the dropwise addition was carried out for 2.75 hours, and the reaction was continued for 1.5 hours at 40 ℃. Then, 120 parts by mass of water was added thereto, and the temperature was reduced to 30 ℃.
(4) And (3) adding 24 parts by mass of a mixed solution of sodium carbonate and sodium bicarbonate (wherein the molar ratio of the sodium carbonate to the sodium bicarbonate is 8:1) into the reactant obtained in the step (3) to adjust the pH value to about 7, thus obtaining the sodium bicarbonate.
The application method of the marine concrete shrinkage-reducing water reducer comprises the following steps: the mixing amount of the water reducing agent in the concrete is 0.8 percent of the weight of the cementing material.
Example 4
A marine concrete reduction type water reducing agent comprises the following steps:
(1) 250 parts by mass (0.1mol) of modified polyether TPEG with the average molecular weight of 2500 is mixed with 103 parts by mass of water in a reactor, and the mixture is stirred at the controlled temperature of 25 ℃ until the mixture is completely dissolved, wherein the concentration of the modified polyether TPEG is 70 percent.
(2) And (2) adding 25 parts by mass of ammonium persulfate into the solution obtained in the step (1), and stirring and reacting for 15 min.
(3) Respectively adding 10 parts by mass of ascorbic acid and 40 parts by mass of a mixed aqueous solution of sodium allylsulfonate (64 parts by mass of water) into the solution obtained in the step (2), wherein the dropwise adding time is 3 hours; then, 14 parts by mass (0.2mol) of an aqueous acrylamide solution (wherein 50 parts by mass of water) was added thereto, the dropping time was 2.8 hours, and the reaction was continued for 1.5 hours at 40 ℃. Then, 120 parts by mass of water was added thereto, and the temperature was reduced to 30 ℃.
(4) And (3) adding 30 parts by mass of a mixed solution of trisodium phosphate and disodium hydrogen phosphate (wherein the molar ratio of the trisodium phosphate to the disodium hydrogen phosphate is 8:1) into the reactant obtained in the step (3), and adjusting the pH value to about 7 to obtain the sodium phosphate-disodium hydrogen phosphate.
The application method of the marine concrete shrinkage-reducing water reducer comprises the following steps: the mixing amount of the water reducing agent in the concrete is 0.8 percent of the weight of the cementing material.
Example 5
A marine concrete reduction type water reducing agent comprises the following steps:
(1) 240 parts by mass (0.1mol) of modified polyether TPEG with the average molecular weight of 2400 and 103 parts by mass of water are mixed in a reactor, and the mixture is stirred at the controlled temperature of 20 ℃ until the mixture is completely dissolved, wherein the concentration of the modified polyether TPEG is 70%.
(2) Adding 25 parts by mass of H to the solution obtained in the step (1)2O2The reaction was stirred for 12 min.
(3) Adding 12 parts by mass of a mixed aqueous solution of ascorbic acid and 40 parts by mass of thioglycolic acid (64 parts by mass of water) into the solution obtained in the step (2), wherein the dropwise adding time is 3 hours; then, 16.7 parts by mass (0.2mol) of an aqueous methacrylic acid solution (wherein 50 parts by mass of water) was added thereto, the dropping time was 2.5 hours, and the reaction was continued for 1 hour at 40 ℃. Then, 120 parts by mass of water was added thereto, and the temperature was reduced to 30 ℃.
(4) And (3) adding 36 parts by mass of a mixed solution of trisodium phosphate and disodium hydrogen phosphate (wherein the molar ratio of the trisodium phosphate to the disodium hydrogen phosphate is 9:1) into the reactant obtained in the step (3), and adjusting the pH value to about 7 to obtain the sodium phosphate-disodium hydrogen phosphate.
The application method of the marine concrete shrinkage-reducing water reducer comprises the following steps: the mixing amount of the water reducing agent in the concrete is 1 percent of the weight of the cementing material.
Example 6
A marine concrete reduction type water reducing agent comprises the following steps:
(1) 240 parts by mass (0.1mol) of modified polyether TPEG with the average molecular weight of 2400 and 103 parts by mass of water are mixed in a reactor, and the mixture is stirred at the controlled temperature of 20 ℃ until the mixture is completely dissolved, wherein the concentration of the modified polyether TPEG is 70%.
(2) Adding 25 parts by mass of H to the solution obtained in the step (1)2O2And the mixture is stirred and reacted for 12min with ammonium persulfate.
(3) Adding 12 parts by mass of ascorbic acid and 40 parts by mass of mixed aqueous solution of thioglycolic acid and mercaptopropionic acid (wherein the mass of water is 64 parts) into the solution obtained in the step (2), and dropwise adding for 3 hours; then, 19.4 parts by mass (0.2mol) of an aqueous methyl methacrylate solution (55 parts by mass of water) was added thereto, and the mixture was dropwise added for 3 hours and allowed to react at 40 ℃ for 1 hour with continued heat preservation. Then, 120 parts by mass of water was added thereto, and the temperature was reduced to 30 ℃.
(4) And (3) adding 36 parts by mass of a mixed solution of trisodium phosphate and disodium hydrogen phosphate (wherein the molar ratio of the trisodium phosphate to the disodium hydrogen phosphate is 10:1) into the reactant obtained in the step (3), and adjusting the pH value to about 7 to obtain the sodium phosphate-disodium hydrogen phosphate.
The application method of the marine concrete shrinkage-reducing water reducer comprises the following steps: the mixing amount of the water reducing agent in the concrete is 0.8 percent of the weight of the cementing material.
Example 7
A marine concrete reduction type water reducing agent comprises the following steps:
(1) 240 parts by mass (0.1mol) of modified polyether TPEG with the average molecular weight of 2400 and 103 parts by mass of water are mixed in a reactor, and the mixture is stirred at the controlled temperature of 20 ℃ until the mixture is completely dissolved, wherein the concentration of the modified polyether TPEG is 70%.
(2) Adding 25 parts by mass of H to the solution obtained in the step (1)2O2The reaction was stirred for 12 min.
(3) Adding 12 parts by mass of ascorbic acid and 40 parts by mass of mixed aqueous solution of thioglycolic acid and mercaptopropionic acid (wherein the mass of water is 64 parts) into the solution obtained in the step (2), and dropwise adding for 3 hours; then, 16.6 parts by mass (0.2mol) of an aqueous methacrylamide solution (wherein 50 parts by mass of water) was added thereto, the dropping time was 3 hours, and the reaction was continued for 1 hour at 40 ℃. Then, 120 parts by mass of water was added thereto, and the temperature was reduced to 30 ℃.
(4) And (3) adding 36 parts by mass of a mixed solution of sodium carbonate and sodium bicarbonate (wherein the molar ratio of the sodium carbonate to the sodium bicarbonate is 10:1) into the reactant obtained in the step (3) to adjust the pH value to about 7, thus obtaining the sodium bicarbonate.
The application method of the marine concrete shrinkage-reducing water reducer comprises the following steps: the mixing amount of the water reducing agent in the concrete is 0.6 percent of the weight of the cementing material.
Comparative example 1
(1) 240 parts by mass (0.1mol) of modified polyether TPEG with the average molecular weight of 2400 and 103 parts by mass of water are mixed in a reactor, and the mixture is stirred at the controlled temperature of 20 ℃ until the mixture is completely dissolved, wherein the concentration of the modified polyether TPEG is 70%.
(2) Adding 25 parts by mass of H to the solution obtained in the step (1)2O2The reaction was stirred for 12 min.
(3) Adding 12 parts by mass of a mixed aqueous solution of ascorbic acid and 40 parts by mass of thioglycolic acid (64 parts by mass of water) into the solution obtained in the step (2), wherein the dropwise adding time is 3 hours; then, 16.7 parts by mass (0.2mol) of an aqueous methacrylic acid solution (wherein 50 parts by mass of water) was added thereto, the dropping time was 2.5 hours, and the reaction was continued for 1 hour at 40 ℃. Then, 120 parts by mass of water was added thereto, and the temperature was reduced to 30 ℃.
(4) And (4) adding 30 parts by mass of 30% sodium hydroxide solution into the reactant obtained in the step (3) to adjust the pH value to about 7, thus obtaining the catalyst.
The application method of the concrete shrinkage-reducing water reducer comprises the following steps: the mixing amount of the water reducing agent in the concrete is 1 percent of the weight of the cementing material.
The surface tension performance test of the water reducing agent obtained in the embodiment and the performance test of the shrinkage ratio and the erosion resistance coefficient of the concrete are as follows:
wherein, the erosion resistance coefficient test is as follows: the ratio of the compressive strength of the concrete test block after curing in 5% sodium sulfate aggressive solution for 6 months to the flexural strength of the concrete test block after curing in pure water for 6 months.
TABLE 1 Performance test results for various examples
Therefore, the water reducing agent of the invention basically keeps the level of the existing water reducing agent in the aspects of shrinkage reduction and water reduction performance, and simultaneously obviously improves the erosion resistance.
The above embodiments are only for assisting understanding of the method of the present application and the core idea thereof, and are not to be construed as limiting the present invention. Those skilled in the art can change, modify, replace and modify the embodiments in the specification according to the idea of the present application.
Claims (7)
1. The marine concrete reduction type water reducing agent is characterized by comprising the following steps:
(1) adding the monomer A into water, stirring and dissolving;
(2) adding peroxide into the solution obtained in the step (1), and uniformly stirring;
(3) respectively adding a mixed aqueous solution of ascorbic acid and a chain transfer agent and a monomer B aqueous solution into the solution obtained in the step (2), carrying out thermal insulation polymerization for 1-1.5h, and then cooling to 30-35 ℃;
(4) adding an anti-erosion component to adjust the pH value of the solution to be neutral, thus obtaining the anti-erosion agent;
the monomer A is one or a mixture of modified polyether TPEG or allyl polyoxyethylene ether HPEG, and the monomer B is one or a mixture of acrylic acid, hydroxyethyl acrylate, hydroxypropyl acrylate, acrylamide, methacrylic acid, methyl methacrylate or methacrylamide;
the anti-erosion component is a mixture of sodium carbonate and sodium bicarbonate or a mixture of trisodium phosphate and disodium hydrogen phosphate;
in the mixture of sodium carbonate and sodium bicarbonate, the molar ratio of the sodium carbonate to the sodium bicarbonate is 5-10: 1; in the mixture of the trisodium phosphate and the disodium hydrogen phosphate, the molar ratio of the trisodium phosphate to the disodium hydrogen phosphate is 8-10: 1;
the mass ratio of the dosage of the anti-erosion component to the monomer A is 0.1-0.15: 1.
2. The marine concrete shrinkage-reducing water reducer as claimed in claim 1, wherein the molar ratio of the monomer A to the monomer B is 1:2-5.5, and the molecular weight of the monomer A is between 2000-2500.
3. The marine concrete reduction water reducer according to claim 1, characterized in that the peroxide is one or a mixture of hydrogen peroxide or ammonium persulfate; the mass ratio of the peroxide to the monomer A is 0.1-0.15: 1.
4. The marine concrete shrinkage-reducing water reducing agent according to claim 1, characterized in that the mass ratio of the ascorbic acid to the monomer A is 0.02-0.05: 1.
5. The marine concrete shrinkage-reducing water reducing agent according to claim 1, wherein the chain transfer agent is a mixture of one or more of sodium allylsulfonate, sodium methallylsulfonate, thioglycolic acid or mercaptopropionic acid; the mass ratio of the using amount of the chain transfer agent to the monomer A is 0.05-0.2: 1.
6. The marine concrete reduction water reducer according to claim 1, wherein in the step (1), the temperature is controlled to be 13-25 ℃ in the stirring and dissolving process, and the concentration of the monomer A is controlled to be 56-70%.
7. The application method of the marine concrete reduction type water reducer as claimed in any one of claims 1 to 6, characterized in that the mixing amount of the water reducer in concrete is 0.6-1.0% of the weight of the cementing material.
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| WO2007099292A1 (en) * | 2006-02-28 | 2007-09-07 | Halliburton Energy Services, Inc. | Salt water stable latex cement slurries |
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| CN100999396A (en) * | 2006-12-29 | 2007-07-18 | 陕西师范大学 | Composition used for improving endurance performance of concrete |
| CN108948288A (en) * | 2018-07-09 | 2018-12-07 | 湖北工业大学 | A kind of cross-linking type polycarboxylate water-reducer preparation method using carboxyl function monomer |
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