CN112708071B - Anti-corrosion ester polycarboxylic acid water reducing agent and preparation method thereof - Google Patents
Anti-corrosion ester polycarboxylic acid water reducing agent and preparation method thereof Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- 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
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B24/00—Use of organic materials as active ingredients for mortars, concrete or artificial stone, e.g. plasticisers
- C04B24/16—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
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- 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
Abstract
The invention relates to the technical field of concrete admixtures, in particular to a corrosion-resistant ester polycarboxylic acid water reducing agent and a preparation method thereof, wherein the corrosion-resistant ester polycarboxylic acid water reducing agent is prepared by an esterification product, an ester macromonomer, acrylic acid, unsaturated sulfonate and a rust-resistant functional monomer B with double bonds, amino groups and sulfur bonds through copolymerization reaction; the esterification product is prepared by esterification reaction of a rust-resistant functional monomer A with amino and hydroxyl, a silane monomer and unsaturated acid. The corrosion-resistant ester polycarboxylate water reducer provided by the invention is prepared by esterifying amino-hydroxyl rust-resistant functional monomer A, silane monomer and unsaturated acid to obtain an esterification product, participating in copolymerization reaction, so that the polycarboxylate water reducer molecule contains silane groups, amino groups and hydroxyl groups, nitrogen atoms in the amino groups and the hydroxyl groups can improve the adsorption capacity with the surface of a reinforcing steel bar and inhibit the electrochemical reaction process on the surface of the reinforcing steel bar, and meanwhile, the amino groups can be combined with H on the surface of a cathode+The cathode reaction rate is reduced, and the corrosion inhibition effect of the reinforcing steel bar is enhanced.
Description
Technical Field
The invention relates to the technical field of concrete admixtures, in particular to a corrosion-resistant ester polycarboxylic acid water reducing agent and a preparation method thereof.
Background
In recent years, with the continuous and rapid development of the economy of China, the construction strength and scale of the infrastructure of China are continuously increased, and the application of concrete members is more and more. The prestressed high-strength concrete pipe pile has the advantages of short construction period, excellent mechanical property, high cost performance, less construction condition limitation and the like, well solves the defects of traditional pile foundations such as a driving type prefabricated solid pile, a drilling cast-in-place pile, a vibrating immersed tube cast-in-place pile and the like, and is widely applied to engineering foundations such as bridges, ports, wharfs and the like.
For marine constructions and buildings in saline-alkali areas, the periphery of the marine constructions and buildings in saline-alkali areas contains a large amount of chloride ions and sulfate ions, which easily generate corrosion effect on reinforced concrete, destroy passive films on the surfaces of reinforcing steel bars, cause corrosion and expansion of the reinforcing steel bars, cause concrete cracking and reduce the actual service life of the engineering.
At present, inorganic salt such as nitrite and the like, alcamines and a migration type rust inhibitor are mainly added to prevent the reinforcing steel bar from being rusted, but the inorganic salt rust inhibitor has the defects that the reinforcing steel bar is corroded by acceleration when the chloride ion concentration is high to a certain degree, the concrete alkali and material reaction is caused to influence the slump, the alcamines and the migration type rust inhibitor have good effects but high cost, and the migration type rust inhibitor is coated on the surface of concrete at the later stage to cause complex construction. Therefore, the polycarboxylate superplasticizer with the rust-resistant function is developed through molecular structure design, and the rust-resistant functional groups are slowly released in the concrete application process to achieve the purpose of steel bar rust resistance, so that the polycarboxylate superplasticizer has important significance.
For example, a patent document with publication number CN107265909B, published in 2020 and 28 years, namely, "a composite sodium silicate/tris (hydroxymethyl) aminomethane reinforced concrete corrosion inhibitor and application thereof" discloses that tris (hydroxymethyl) aminomethane and sodium silicate respectively play a role in isolation and inhibition to form double protection on a steel bar, wherein the organic component tris (hydroxymethyl) aminomethane can be adsorbed on the surface of the steel bar to form an adsorption film to prevent the steel bar from being corroded by chloride ions; and the inorganic component sodium silicate can promote the surface of the steel bar to form a compact passive film to prevent further oxidation.
For example, patent document CN104327221B, published 2017, 08 and 25, entitled "a polycarboxylic acid water reducing agent for anti-rust hydraulic engineering and preparation method thereof" discloses copolymerization reaction of methallyl polyoxyethylene allyl ether, water, acrylic acid, and maleic acid tetrazole, with maleic acid triethoxy silane propylamine and molecular weight regulator, and initiator; the water reducing agent has high water reducing rate, and good corrosion resistance and shrinkage rate of the steel bar. However, the method needs 2 times of independent preparation of functional monomers for copolymerization reaction, the operation steps are relatively complex, the use amount of the functional monomers is large, the cost is high, and the obtained product has relatively short special functions such as early strength and the like besides the water reducing and slump retaining performance and the rust resistance.
Disclosure of Invention
In order to solve the problem that reinforcing steel bars of marine engineering and saline-alkali land buildings are easy to corrode in the background art, the invention provides a corrosion-resistant ester polycarboxylic acid water reducing agent, which is prepared from an esterification product, an ester macromonomer, acrylic acid, unsaturated sulfonate and a rust-resistant functional monomer B with double bonds, amino groups and sulfur bonds through copolymerization;
the esterification product is prepared by performing esterification reaction on a rust-resistant functional monomer A with amino and hydroxyl, a silane monomer and unsaturated acid.
Further, the polymerization inhibitor for the esterification reaction is at least one of 4-hydroxypiperidinol oxygen free radical, 4-tert-butyl catechol and methyl hydroquinone; the catalyst is a supported solid acid catalyst, preferably SO4 2-/SiO2-TiO2。
Further, the temperature of the esterification reaction is 70-130 ℃, and the time is 3-5 h.
Further, the rust-resistant functional monomer A is trihydroxymethyl aminomethane; the silane monomer is N-aminoethyl-3-aminopropyltriethoxysilane.
Further, the unsaturated acid is one of acrylic acid and methacrylic acid.
Furthermore, the molar ratio of the rust-resistant functional monomer A to the silane monomer to the unsaturated acid is 1:1: 2-5, the amount of the catalyst is 0.5-2% of the total mass of the unsaturated acid, the rust-resistant functional monomer A and the silane monomer, and the amount of the polymerization inhibitor is 0.5-2.5% of the total mass of the unsaturated acid, the rust-resistant functional monomer A and the silane monomer.
Furthermore, the rust-resistant functional monomer B is allylthiourea, and the allylthiourea is introduced to participate in copolymerization reaction, so that lone pair electrons with S in the polycarboxylate superplasticizer molecule can form a complex adsorption film with Fe hollow orbit, and harmful substances are isolated from contacting with reinforcing steel bars, thereby further improving the corrosion-resistant effect.
Further, the ester macromonomer is one of polyethylene glycol monoacrylate, polyethylene glycol monomethacrylate, polyethylene glycol monomethoxy ether monoacrylate and polyethylene glycol monomethoxy ether monomethacrylate with the molecular weight of 3000-5000.
Further, the unsaturated sulfonate is one of sodium methallyl sulfonate and 3-allyloxy-2-hydroxy-1-propane sodium sulfonate.
Further, the copolymerization reaction also comprises an oxidant, a reducing agent and a chain transfer agent, wherein the dosage of the oxidant is 1% -3% of the total mass of the ester macromonomer, the dosage of the reducing agent is 0.5% -2% of the total mass of the ester macromonomer, and the dosage of the chain transfer agent is 0.5% -2.5% of the total mass of the ester macromonomer.
Further, the oxidant is ammonium persulfate, potassium persulfate, sodium persulfate or hydrogen peroxide.
Further, the reducing agent is 2-hydroxy-2-sulfinato acetic acid, 2-hydroxy-2-sulfinato acetic acid disodium salt, 2-hydroxy-2-sulfonato acetic acid or 2-hydroxy-2-sulfonato acetic acid disodium salt.
Further, the copolymerization reaction chain transfer agent is thioglycolic acid, mercaptoethanol, 3-mercaptopropionic acid, isooctyl 3-mercaptopropionate and trisodium phosphate.
Further, the mass ratio of the esterification product to the ester macromonomer to the acrylic acid to the unsaturated sulfonate to the rust-resistant functional monomer B is 2-5: 100: 4-8: 2-4: 0.5-2.
The invention also provides a preparation method of the corrosion-resistant ester polycarboxylic acid water reducing agent, wherein
And (3) carrying out copolymerization reaction on the esterification product, the ester macromonomer, acrylic acid, unsaturated sulfonate and the rust-resistant functional monomer B to obtain the corrosion-resistant ester polycarboxylic acid water reducer.
Further, the copolymerization reaction temperature is normal temperature.
Further, the pH of the corrosion-resistant ester-based polycarboxylic acid water reducing agent is 6 to 7.
Compared with the prior art, the corrosion-resistant ester polycarboxylic acid water reducing agent provided by the invention has the following technical principles and beneficial effects:
1. esterification products prepared by esterifying amino and hydroxyl rust-resistant functional monomer A, silane monomer and unsaturated acid are used for participating in the next copolymerization reaction, so that the polycarboxylate superplasticizer has silane groups, amino groups and hydroxyl groups in molecules, nitrogen atoms and hydroxyl groups in the amino groups can improve the adsorption capacity with the surface of a reinforcing steel bar and inhibit the electrochemical reaction process on the surface of the reinforcing steel bar, and meanwhile, the amino groups can be combined with H on the surface of a cathode+The cathode reaction rate is reduced, and the corrosion inhibition effect of the reinforcing steel bar is enhanced.
2. The introduction of the silane monomer can be firmly combined on the surface and in the cavity of the concrete to prevent harmful ions from permeating into the concrete, and the polycarboxylic acid water reducing agent with the silane monomer has important contribution to the improvement of the strength of the tubular pile concrete under steam curing and steam pressure conditions.
3. Ester macromonomers are adopted to participate in copolymerization reaction, so that the prepared polycarboxylic acid water reducing agent has better slump retaining property and workability.
4. The invention has simple process operation, mild reaction conditions and easy large-scale production, and simultaneously solves the problems that the two performances are mutually influenced and the superposition effect is not ideal when the existing water reducing agent and the rust inhibitor are compounded to obtain the rust-resistant water reducing agent.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the following description will clearly and completely describe the embodiments of the present invention, and obviously, the described embodiments are a part of the embodiments of the present invention, but not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The invention also provides a preparation method of the corrosion-resistant ester polycarboxylic acid water reducing agent, which comprises the following steps:
(1) adding unsaturated acid, a rust-resistant functional monomer A and a silane monomer into a reaction container, mixing, adding a catalyst and a polymerization inhibitor under a vacuum condition, adjusting the temperature to 70-130 ℃, and reacting for 3-5 hours to obtain an esterification product;
(2) and adding the esterification product and the ester macromonomer into a reaction container, mixing, then respectively dropwise adding an initiator solution, a chain transfer agent solution, an acrylic acid, unsaturated sulfonate and rust-resistant functional monomer B mixed solution, reacting for 1.5-2 h at normal temperature, keeping the temperature for a period of time after the reaction is finished, and adding 32% liquid caustic soda to adjust the pH value to 6-7, thus obtaining the anti-corrosion ester polycarboxylic acid water reducer.
The invention also provides the following embodiments:
example 1
(1) Preparing an esterification product: 89.2 parts by weight of acrylic acid, 50 parts by weight of tris (hydroxymethyl) aminomethane and 109 parts by weight of N-aminoethyl-3-aminopropyltriethoxysilane are added into a first reaction vessel and mixed, and 2.97 parts by weight of a supported solid acid catalyst SO is added under a vacuum condition4 2-/SiO2-TiO22.97 parts of methyl hydroquinone, and adjusting the reaction temperature to 110 ℃ for 4 hours to obtain an esterification product;
(2) and (3) copolymerization reaction: adding 3.5 parts by weight of the esterification product prepared in the step (1), 100 parts by weight of monomethoxy ether monomethacrylate polyethylene glycol with the molecular weight of 5000 and 111 parts by weight of water into a second reaction vessel, uniformly stirring, and uniformly mixing 2.5 parts by weight of hydrogen peroxide and 20 parts by weight of water in a first dripping device; 1 part of 2-hydroxy-2-sulfinato acetic acid, 1.5 parts of 3-mercaptopropionic acid and 20 parts of water are uniformly mixed in a second dripping device; 4 parts of acrylic acid, 4 parts of sodium methallyl sulfonate, 2 parts of allylthiourea and 20 parts of water are uniformly mixed in a third dripping device; at normal temperature, sequentially dripping the materials in the first dripping device, the second dripping device and the third dripping device into the second reaction container, dripping the materials in the third dripping device, the second dripping device and the first dripping device in 1.5h, and reacting at constant temperature for 0.5 h;
(3) and adding 12 parts by weight of 32% sodium hydroxide by mass to obtain the corrosion-resistant ester polycarboxylic acid water reducer with the concentration of 40%.
Example 2
(1) Preparing an esterification product: adding 60 parts by weight of acrylic acid, 50 parts by weight of tris (hydroxymethyl) aminomethane and 109 parts by weight of N-aminoethyl-3-aminopropyltriethoxysilane into a first reaction vessel, mixing, adding 4.3 parts by weight of a supported solid acid catalyst SO42-/SiO2-TiO2 and 5.4 parts by weight of 4-hydroxypiperidinol oxygen free radicals under a vacuum pumping condition, adjusting the reaction temperature to 90 ℃, and reacting for 5 hours to obtain an esterification product;
(2) and (3) copolymerization reaction: adding 2 parts by weight of the esterification product prepared in the step (1), 100 parts by weight of polyethylene glycol monomethoxy ether monoacrylate with the molecular weight of 3000 and 108 parts by weight of water into a second reaction vessel, uniformly stirring, and uniformly mixing 3 parts by weight of ammonium persulfate and 20 parts by weight of water in a first dripping device; 2 parts of disodium 2-hydroxy-2-sulfinato acetate, 0.5 part of mercaptoethanol and 20 parts of water are uniformly mixed in a second dripping device; 5 parts of acrylic acid, 3 parts of sodium methallyl sulfonate, 1 part of allylthiourea and 20 parts of water are uniformly mixed in a third dripping device; at normal temperature, sequentially dripping the materials in the first dripping device, the second dripping device and the third dripping device into the second reaction container, dripping the materials in the third dripping device, the second dripping device and the first dripping device in 1.5h, and reacting at constant temperature for 0.5 h;
(3) and adding 12 parts by weight of 32% sodium hydroxide by mass to obtain the corrosion-resistant ester polycarboxylic acid water reducer with the concentration of 40%.
Example 3
(1) Preparing an esterification product: 177.6 parts of methacrylic acid, 50 parts of tris (hydroxymethyl) aminomethane and 109 parts of N-aminoethyl-3-aminopropyltriethoxysilane are added into a first reaction vessel to be mixed according to parts by weight, 1.68 parts of a supported solid acid catalyst SO42-/SiO2-TiO2 and 1.68 parts of 4-hydroxypiperidinol oxygen free radicals are added under the condition of vacuum pumping, the reaction temperature is adjusted to 100 ℃, and the esterification product is obtained after 3 hours of reaction;
(2) and (3) copolymerization reaction: adding 5 parts by weight of the esterification product prepared in the step (1), 100 parts by weight of polyethylene glycol monomethacrylate with the molecular weight of 3000 and 113 parts by weight of water into a second reaction vessel, uniformly stirring, and uniformly mixing 1 part by weight of sodium persulfate and 20 parts by weight of water in a first dripping device; 0.5 part of 2-hydroxy-2-sulfonic acid disodium acetate, 2.5 parts of trisodium phosphate and 20 parts of water are uniformly mixed in a second dripping device; 8 parts of acrylic acid, 2 parts of 3-allyloxy-2-hydroxy-1-propane sodium sulfonate, 0.5 part of allylthiourea and 20 parts of water are uniformly mixed in a third dripping device; at normal temperature, sequentially dripping the materials in the first dripping device, the second dripping device and the third dripping device into the second reaction container, dripping the materials in the third dripping device, the second dripping device and the first dripping device in 1.5h, and reacting at constant temperature for 0.5 h;
(3) and adding 12 parts by weight of 32% sodium hydroxide by mass to obtain the corrosion-resistant ester polycarboxylic acid water reducer with the concentration of 40%.
The invention also provides the following comparative examples:
comparative example 1
Selecting high-performance reinforcing agent and Subot of commercially available Point-GS type pile rod concrete
And (3) compounding the ZX (II) reinforced concrete rust inhibitor with the dosage of 0.2 percent and 5 percent of the cementing material respectively for concrete verification.
Comparative example 2
(1) Preparing an esterification product: 89.2 parts of acrylic acid and 109 parts of N-aminoethyl-3-aminopropyltriethoxysilane are added into a first reaction vessel for mixing, and 2.97 parts of supported solid acid catalyst SO are added under the condition of vacuum pumping4 2-/SiO2-TiO22.97 parts of methyl hydroquinone, and adjusting the reaction temperature to 110 ℃ for 4 hours to obtain an esterification product;
(2) and (3) copolymerization reaction: adding 3.5 parts by weight of the esterification product prepared in the step (1), 100 parts by weight of monomethoxy ether monomethacrylate polyethylene glycol with the molecular weight of 5000 and 111 parts by weight of water into a second reaction vessel, uniformly stirring, and uniformly mixing 2.5 parts by weight of hydrogen peroxide and 20 parts by weight of water in a first dripping device; 1 part of 2-hydroxy-2-sulfinato acetic acid, 1.5 parts of 3-mercaptopropionic acid and 20 parts of water are uniformly mixed in a second dripping device; 4 parts of acrylic acid, 4 parts of sodium methallyl sulfonate, 2 parts of allylthiourea and 20 parts of water are uniformly mixed in a third dripping device; at normal temperature, sequentially dripping the materials in the first dripping device, the second dripping device and the third dripping device into the second reaction container, dripping the materials in the third dripping device, the second dripping device and the first dripping device in 1.5h, and reacting at constant temperature for 0.5 h;
(3) and adding 12 parts by weight of 32% sodium hydroxide by mass to obtain the corrosion-resistant ester polycarboxylic acid water reducer with the concentration of 40%.
(4) The water reducing agent and the trihydroxymethyl aminomethane in the comparative example 2 are selected, and the dosage of the water reducing agent and the trihydroxymethyl aminomethane is respectively 0.2 percent and 1.2 percent of the cementing material for compounding and concrete verification.
Comparative example 3
(1) Preparing an esterification product: according to parts by weight, 89.2 parts of acrylic acid, 50 parts of 2-amino-2-methyl-1-propanol and 109 parts of N-aminoethyl-3-aminopropyltriethoxysilane are added into a first reaction vessel for mixing, and 2.97 parts of supported solid acid catalyst SO is added under the condition of vacuum pumping4 2-/SiO2-TiO22.97 parts of methyl hydroquinone, and adjusting the reaction temperature to 110 ℃ for 4 hours to obtain an esterification product;
(2) and (3) copolymerization reaction: adding 3.5 parts by weight of the esterification product prepared in the step (1), 100 parts by weight of monomethoxy ether monomethacrylate polyethylene glycol with the molecular weight of 5000 and 111 parts by weight of water into a second reaction vessel, uniformly stirring, and uniformly mixing 2.5 parts by weight of hydrogen peroxide and 20 parts by weight of water in a first dripping device; 1 part of 2-hydroxy-2-sulfinato acetic acid, 1.5 parts of 3-mercaptopropionic acid and 20 parts of water are uniformly mixed in a second dripping device; 4 parts of acrylic acid, 4 parts of sodium methallyl sulfonate, 2 parts of allylthiourea and 20 parts of water are uniformly mixed in a third dripping device; at normal temperature, sequentially dripping the materials in the first dripping device, the second dripping device and the third dripping device into the second reaction container, dripping the materials in the third dripping device, the second dripping device and the first dripping device in 1.5h, and reacting at constant temperature for 0.5 h;
(3) and adding 12 parts by weight of 32% sodium hydroxide by mass to obtain the corrosion-resistant ester polycarboxylic acid water reducer with the concentration of 40%.
Comparative example 4
(1) Preparing an esterification product: 89.2 parts of acrylic acid, 50 parts of tris (hydroxymethyl) aminomethane and 109 parts of gamma-aminopropyltriethoxysilane are added into a first reaction vessel to be mixed in parts by weight, and 2.97 parts of a supported solid acid catalyst SO are added under the condition of vacuum pumping4 2-/SiO2-TiO22.97 parts of methyl hydroquinone, and adjusting the reaction temperature to 110 ℃ for 4 hours to obtain an esterification product;
(2) and (3) copolymerization reaction: adding 3.5 parts by weight of the esterification product prepared in the step (1), 100 parts by weight of monomethoxy ether monomethacrylate polyethylene glycol with the molecular weight of 5000 and 111 parts by weight of water into a second reaction vessel, uniformly stirring, and uniformly mixing 2.5 parts by weight of hydrogen peroxide and 20 parts by weight of water in a first dripping device; 1 part of 2-hydroxy-2-sulfinato acetic acid, 1.5 parts of 3-mercaptopropionic acid and 20 parts of water are uniformly mixed in a second dripping device; 4 parts of acrylic acid, 4 parts of sodium methallyl sulfonate, 2 parts of allylthiourea and 20 parts of water are uniformly mixed in a third dripping device; at normal temperature, sequentially dripping the materials in the first dripping device, the second dripping device and the third dripping device into the second reaction container, dripping the materials in the third dripping device, the second dripping device and the first dripping device in 1.5h, and reacting at constant temperature for 0.5 h;
(3) and adding 12 parts by weight of 32% sodium hydroxide by mass to obtain the corrosion-resistant ester polycarboxylic acid water reducer with the concentration of 40%.
Comparative example 5
(1) Preparing an esterification product: 89.2 parts by weight of acrylic acid, 50 parts by weight of tris (hydroxymethyl) aminomethane and 109 parts by weight of N-aminoethyl-3-aminopropyltriethoxysilane are added into a first reaction vessel and mixed, and 2.97 parts by weight of negative ions are added under a vacuum conditionSupported solid acid catalyst SO4 2-/SiO2-TiO22.97 parts of methyl hydroquinone, and adjusting the reaction temperature to 110 ℃ for 4 hours to obtain an esterification product;
(2) and (3) copolymerization reaction: adding 3.5 parts by weight of the esterification product prepared in the step (1), 100 parts by weight of monomethoxy ether monomethacrylate polyethylene glycol with the molecular weight of 5000 and 108 parts by weight of water into a second reaction vessel, uniformly stirring, and uniformly mixing 2.5 parts by weight of hydrogen peroxide and 20 parts by weight of water in a first dripping device; 1 part of 2-hydroxy-2-sulfinato acetic acid, 1.5 parts of 3-mercaptopropionic acid and 20 parts of water are uniformly mixed in a second dripping device; 4 parts of acrylic acid, 4 parts of sodium methallyl sulfonate and 20 parts of water are uniformly mixed in a third dripping device; at normal temperature, sequentially dripping the materials in the first dripping device, the second dripping device and the third dripping device into the second reaction container, dripping the materials in the third dripping device, the second dripping device and the first dripping device in 1.5h, and reacting at constant temperature for 0.5 h;
(3) and adding 12 parts by weight of 32% sodium hydroxide by mass to obtain the corrosion-resistant ester polycarboxylic acid water reducer with the concentration of 40%.
Comparative example 6
(1) Preparing an esterification product: 89.2 parts of acrylic acid and 50 parts of tris (hydroxymethyl) aminomethane are added into a first reaction vessel and mixed, and 2.97 parts of supported solid acid catalyst SO is added under the condition of vacuum pumping4 2-/SiO2-TiO22.97 parts of methyl hydroquinone, and adjusting the reaction temperature to 110 ℃ for 4 hours to obtain an esterification product;
(2) and (3) copolymerization reaction: adding 3.5 parts by weight of the esterification product prepared in the step (1), 2 parts by weight of 3- (methacryloyloxy) propyl trimethoxy silane, 100 parts by weight of 5000 parts by weight of monomethoxy ether monomethacrylate polyethylene glycol ester and 111 parts by weight of water into a second reaction vessel, uniformly stirring, and uniformly mixing 2.5 parts by weight of hydrogen peroxide and 20 parts by weight of water in a first dripping device; 1 part of 2-hydroxy-2-sulfinato acetic acid, 1.5 parts of 3-mercaptopropionic acid and 20 parts of water are uniformly mixed in a second dripping device; 4 parts of acrylic acid, 4 parts of sodium methallyl sulfonate, 2 parts of allylthiourea and 20 parts of water are uniformly mixed in a third dripping device; at normal temperature, sequentially dripping the materials in the first dripping device, the second dripping device and the third dripping device into the second reaction container, dripping the materials in the third dripping device, the second dripping device and the first dripping device in 1.5h, and reacting at constant temperature for 0.5 h;
(3) and adding 12 parts by weight of 32% sodium hydroxide by mass to obtain the corrosion-resistant ester polycarboxylic acid water reducer with the concentration of 40%.
Comparing the ether polycarboxylic acid water reducing agent special for the corrosion-resistant pipe pile synthesized in the examples 1-3 with the pipe pile concrete for the comparative examples 1-6, adopting conch PO52.5R cement, wherein the mixing amount of the water reducing agent in the examples 1-2 is 0.15 percent (folded solid part) of the cementing material, the mixing amount of the water reducing agent in the comparative examples 3-6 is 0.2 percent (folded solid part) of the cementing material, and the mixing amount of the admixture in the comparative examples 1-2 refers to a specific compound formula. The performance of the pipe pile is tested according to GB13476-2009 Pre-tensioning prestressed concrete pipe pile, and the slump, the expansion degree and the like of the pipe pile are tested according to GB 8076-2008 concrete admixture, and the performance of the concrete is tested according to GB/T31296-2014 concrete corrosion and rust inhibitor. The concrete mixing proportion is as follows: 308kg/m cement344kg/m of mineral powder388kg/m of fine sand3Coarse sand 384kg/m3Fine sand 384kg/m3345kg/m of large stone3805kg/m of small stone3The initial slump was controlled to 190. + -. 10mm, and the concrete test results are shown in Table 1.
Table 1 pipe pile concrete performance data
The test results in the table 1 show that the performances of the examples are superior to those of the comparative examples, and the results of the examples and the comparative example 1 show that compared with the mode of compounding the existing water reducing agent with the rust inhibitor, the corrosion-resistant ester polycarboxylic acid water reducing agent provided by the invention has better rust inhibiting function and better workability, improves the steam-curing and steam-pressure strength of the pipe pile concrete and improves the slump retaining performance of the concrete;
the combination of the comparative example 2 shows that the polycarboxylate water reducer prepared by directly participating in copolymerization after the rust-resistant functional monomer A is subjected to esterification reaction is superior to the rust-resistant water reducer prepared by directly compounding the rust-resistant functional monomer A and the water reducer in the aspects of rust resistance and water reducing performance;
compared with other types of existing rust-resistant functional monomers and silane monomers, the rust-resistant functional monomer A and the silane monomer provided by the invention have better corrosion inhibition performance and water reduction performance;
according to the comparison example 5, the polycarboxylic acid water reducing agent prepared by adding the rust-resistant functional monomer B can improve the corrosion resistance effect of the tubular pile.
Compared with the water reducing agent prepared by directly copolymerizing unsaturated silane monomers containing double bonds, the water reducing agent prepared by the method disclosed by the invention has the advantages that the silane monomers are esterified to prepare the esterification product containing the silane bonds and then copolymerized, so that the silane monomers can be firmly combined on the surface and cavities of concrete, harmful ions are prevented from permeating, and meanwhile, the corrosion resistance and the pipe pile concrete strength under steam curing and steam pressure conditions are improved.
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.
Claims (7)
1. The corrosion-resistant ester polycarboxylic acid water reducing agent is characterized by being prepared from an esterification product, an ester macromonomer, acrylic acid, unsaturated sulfonate and a rust-resistant functional monomer B with double bonds, amino and sulfur bonds through copolymerization reaction;
the esterification product is prepared by performing esterification reaction on a rust-resistant functional monomer A with amino and hydroxyl, a silane monomer and unsaturated acid;
the rust-resistant functional monomer A is trihydroxymethyl aminomethane;
the silane monomer is N-aminoethyl-3-aminopropyltriethoxysilane;
the mole ratio of the rust-resistant functional monomer A to the silane monomer to the unsaturated acid is 1:1: 2-5;
the rust-resistant functional monomer B is allyl thiourea;
the ester macromonomer is one of polyethylene glycol monoacrylate, polyethylene glycol monomethacrylate, polyethylene glycol monomethoxy ether monoacrylate and polyethylene glycol monomethoxy ether monomethacrylate, wherein the molecular weight of the ester macromonomer is 3000-5000;
the mass ratio of the esterification product to the ester macromonomer to the acrylic acid to the unsaturated sulfonate to the rust-resistant functional monomer B is 2-5: 100: 4-8: 2-4: 0.5-2.
2. The anti-corrosion ester-based polycarboxylic acid water reducing agent according to claim 1, characterized in that: the unsaturated acid is one of acrylic acid and methacrylic acid.
3. The anti-corrosion ester-based polycarboxylic acid water reducing agent according to claim 1, characterized in that: the polymerization inhibitor for the esterification reaction is at least one of 4-hydroxypiperidinol oxygen free radical, 4-tert-butyl catechol and methyl hydroquinone; the catalyst is a supported solid acid catalyst.
4. The anti-corrosion ester-based polycarboxylic acid water reducing agent according to claim 1, characterized in that: the unsaturated sulfonate is one of sodium methallyl sulfonate and 3-allyloxy-2-hydroxy-1-propane sodium sulfonate.
5. The anti-corrosion ester-based polycarboxylic acid water reducing agent according to claim 1, characterized in that: the chain transfer agent for copolymerization reaction is thioglycolic acid, mercaptoethanol, 3-mercaptopropionic acid, isooctyl 3-mercaptopropionate and trisodium phosphate;
the initiator of the copolymerization reaction comprises an oxidant and a reducing agent, wherein the oxidant is ammonium persulfate, potassium persulfate, sodium persulfate or hydrogen peroxide; the reducing agent is 2-hydroxy-2-sulfinato acetic acid, 2-hydroxy-2-sulfinato acetic acid disodium salt, 2-hydroxy-2-sulfonato acetic acid or 2-hydroxy-2-sulfonato acetic acid disodium salt.
6. The anti-corrosion ester-based polycarboxylic acid water reducing agent according to claim 5, characterized in that: the copolymerization reaction also comprises that the dosage of the oxidant is 1-3% of the total mass of the ester macromonomer, the dosage of the reducing agent is 0.5-2% of the total mass of the ester macromonomer, and the dosage of the chain transfer agent is 0.5-2.5% of the total mass of the ester macromonomer.
7. A method for producing a corrosion-resistant ester-based polycarboxylic acid water reducing agent according to any one of claims 1 to 6,
and (3) carrying out copolymerization reaction on the esterification product, the ester macromonomer, acrylic acid, unsaturated sulfonate and the rust-resistant functional monomer B to obtain the corrosion-resistant ester polycarboxylic acid water reducer.
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