CN112708069A - Ester polycarboxylic acid water reducing agent with rust resistance function and preparation method thereof - Google Patents
Ester polycarboxylic acid water reducing agent with rust resistance function 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
- C04B24/24—Macromolecular compounds
- C04B24/26—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- C04B24/2688—Copolymers containing at least three different monomers
- C04B24/2694—Copolymers containing at least three different monomers containing polyether side chains
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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 an ester polycarboxylic acid water reducing agent with a rust-resistant function and a preparation method thereof, wherein the ester polycarboxylic acid water reducing agent is prepared by an esterification product, an ester macromonomer, acrylic acid, an unsaturated polyhydroxy monomer and a rust-resistant functional monomer B with double bonds, amino groups and sulfur bonds through copolymerization reaction; the esterification product isThe rust-resistant functional monomer A with benzene ring and hydroxyl and unsaturated acid are prepared by esterification reaction. The ester polycarboxylate superplasticizer with the rust-resistant function provided by the invention is prepared by esterifying a rust-resistant functional monomer A containing benzene ring and hydroxyl with unsaturated acid to obtain an esterification product, participating in the next copolymerization reaction, so that the polycarboxylate superplasticizer has groups such as benzene ring, amino group, hydroxyl group and the like in the molecule, the nitrogen atom and the hydroxyl group in the amino group 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 group 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 an ester polycarboxylic acid water reducing agent with a rust-resistant function 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, publication No. CN108069634B, published on 2020, 08 and 07, entitled "a steel bar rust inhibitor containing Gemini amino ester" discloses that a three-dimensional protective film with optimized structure formed by combining Gemini amino ester, organic amine and acid can form passivation film, deposition film and adsorption film on the surface of steel bar, thereby achieving the rust inhibiting effect. When the rust inhibitor is applied to concrete engineering, a compound water reducing agent is required to be used, so that the two performances are inevitably influenced with each other, the superposition effect is not ideal, the compatibility is not good, and the like;
for example, in the patent document with the publication number CN109679035A, published 2019, 04, 26 and named as "a corrosion-resistant and rust-resistant polycarboxylic acid water reducer and a preparation method thereof", an unsaturated polyether macromonomer, an unsaturated acid monomer, an anticorrosive functional monomer propenyl-benzyl diethylene triamine, a rust-resistant functional monomer triethanolamine monooleate, an initiator, a reducing agent and deionized water are subjected to copolymerization reaction, amino and hydroxyl groups are introduced into a molecular chain segment, and although the rust-resistant capability is improved to a certain extent, the water reducing and slump retaining effects of the water reducer are poor, and the step for preparing the anticorrosive functional monomer propenyl-benzyl diethylene triamine monomer is complicated.
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 an ester polycarboxylic acid water reducing agent with a rust-resisting function, wherein the ester polycarboxylic acid water reducing agent is prepared from an esterification product, an ester macromonomer, acrylic acid, an unsaturated polyhydroxy monomer and a rust-resisting functional monomer B with double bonds, amino and sulfur bonds through copolymerization;
the esterification product is prepared by esterification reaction of a rust-resistant functional monomer A with a benzene ring and a hydroxyl group and an unsaturated acid.
Further, the unsaturated polyhydroxy monomer is 3- (2,3, 4-trihydroxyphenyl) -2-acrylic acid, and has the following structural formula:
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 reaction lasts for 3-5 hours.
Further, the rust-resistant functional monomer A is N- [2- (2-hydroxyethoxy) -4-nitrophenyl ] ethanolamine and has the following structural formula:
further, the unsaturated acid is one of acrylic acid and methacrylic acid.
Further, the molar ratio of the rust-resistant functional monomer A to the unsaturated acid is 1: 1-4, the dosage of the catalyst is 0.5-2% of the total mass of the unsaturated acid and the rust-resistant functional monomer A, and the dosage of the polymerization inhibitor is 0.5-2% of the total mass of the unsaturated acid and the rust-resistant functional monomer A.
Further, the rust-resistant functional monomer B is allyl thiourea. According to the invention, 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, harmful substances are isolated from contacting with reinforcing steel bars, and the rust inhibition effect is further improved.
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 1200-3000.
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, thioglycerol, isooctyl 3-mercaptopropionate and trisodium phosphate.
Further, the mass ratio of the esterification product, the ester macromonomer, the acrylic acid, the rust-resistant functional monomer B and the unsaturated polyhydroxy monomer is 2-5: 100: 5-10: 0.5-2: 2-4.
The invention also provides a preparation method of the ester polycarboxylic acid water reducing agent with the rust-resisting function, wherein
And (3) carrying out copolymerization reaction on the esterification product, the ester macromonomer, acrylic acid, the unsaturated polyhydroxy monomer and the rust-resistant functional monomer B to obtain the ester polycarboxylic acid water reducer with the rust-resistant function.
Further, the copolymerization reaction temperature is normal temperature.
Further, the pH value of the ester type polycarboxylic acid water reducing agent with the rust-resistant function is 6-7.
Compared with the prior art, the ester polycarboxylic acid water reducing agent with the rust-resistant function provided by the invention has the following technical principles and beneficial effects:
1. an esterification product prepared by esterifying a rust-resistant functional monomer A containing benzene rings and hydroxyl with unsaturated acid participates in the next copolymerization reaction, so that the polycarboxylate superplasticizer molecules contain benzene rings, amino groups, hydroxyl groups and other groups, nitrogen atoms in the amino groups and the hydroxyl groups can improve the adsorption capacity with the surface of a steel bar and inhibit the electrochemical reaction process on the surface of the steel bar, and meanwhile, the amino groups can be combined with H & lt + & gt on the surface of a cathode, so that the reaction rate of the cathode is reduced, and the corrosion inhibition effect of the steel bar is enhanced; the benzene ring is used as a rigid aromatic group with large steric hindrance, and a special adsorption barrier film with 3d three-dimensional space distribution is formed on the surface of the metal, so that the thickness of the barrier film is increased, and the rust resistance and corrosion inhibition effects of the steel bar are improved.
2. The dihydroxy in the partial rust-resistant functional monomer A is esterified to obtain a monomer which is a cross-linking monomer, partial cross-linking is realized in the polymerization process, and the steric hindrance effect of the system is increased; under the alkaline condition of cement, the hydrolysis of a cross-linking structure is slower than that of a water reducing agent obtained by copolymerization of monomers containing ester groups, acid anhydrides and other groups, and the hydrolysis is gradually carried out along with the prolonging of time to continuously release carboxylic acid groups which are beneficial to improving the water reducing effect, so that the lost water reducing rate is compensated, and the effect of maintaining slump is achieved.
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. Unsaturated polyhydroxy monomers are introduced to participate in copolymerization reaction, so that a polycarboxylic acid molecular structure is provided with a rigid benzene ring and a polyhydroxy structure, and the end face adsorption of clay is resisted by utilizing the benzene ring structure with larger size, so that the intercalation adsorption is avoided; the hydroxyl and water form hydrogen bonds, are preferentially adsorbed on the surface and the layers of the montmorillonite, occupy a large number of active sites, reduce the adsorption of the polycarboxylate water reducing agent, highly disperse cement particles and further achieve the effect of inhibiting the negative influence of the montmorillonite.
5. The method has the advantages of simple process operation, mild reaction conditions and easy large-scale production, and simultaneously solves the problems that the water reducing agent and the rust inhibitor in the prior art are subjected to mutual influence and the superposition effect is not ideal when the rust-resistant water reducing agent and the rust inhibitor are obtained in a compounding manner.
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 ester polycarboxylic acid water reducing agent with the rust-resisting function, which comprises the following steps:
(1) adding unsaturated acid and a rust-resistant functional monomer A into a reaction container, mixing, adding a catalyst and a polymerization inhibitor under a vacuum condition, adjusting the temperature to be 70-130 ℃, and reacting for 3-5 hours to obtain an esterification product;
(2) adding the esterification product and the ester macromonomer into a reaction vessel for mixing, then respectively dropwise adding an initiator solution, a chain transfer agent solution, an acrylic acid, unsaturated polyhydroxy monomer 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, adding 32% liquid caustic soda to adjust the pH value to 6-7, and obtaining the anti-corrosion type ester polycarboxylic acid water reducer special for the tubular pile
The invention also provides the following embodiments:
example 1
(1) Preparing an esterification product: according to the parts by weight, 37.18 parts of acrylic acid and 50 parts of N- [2- (2-hydroxyethoxy) -4-nitrophenyl]Ethanolamine is added into a first reaction container for mixing, and 1.74 parts of supported solid acid catalyst SO is added under the condition of vacuum pumping4 2-/SiO2-TiO20.44 part of methyl hydroquinone, and adjusting the reaction temperature to 110 ℃ for 4 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 2000-molecular-weight monomethoxy ether-monomethacrylate polyethylene glycol ester and 114 parts by weight of water into a second reaction vessel, uniformly stirring, and uniformly mixing 3 parts by weight of potassium persulfate and 20 parts by weight of water in a first dripping device; 1 part of 2-hydroxy-2-sulfonic acid disodium acetate, 2.5 parts of mercaptoethanol and 20 parts of water are uniformly mixed in a second dripping device; 7 parts of acrylic acid, 2 parts of allylthiourea, 3 parts of 3- (2,3, 4-trihydroxyphenyl) -2-acrylic acid 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 mass percent sodium hydroxide to obtain the ester polycarboxylic acid water reducer with the rust-resistant function, wherein the concentration of the ester polycarboxylic acid water reducer is 40%.
Example 2
(1) Preparing an esterification product: according to the parts by weight, 14.87 parts of acrylic acid and 50 parts of N- [2- (2-hydroxyethoxy) -4-nitrophenyl]Ethanolamine is added into a first reaction container for mixing, and 0.65 part of supported solid acid catalyst SO is added under the condition of vacuum pumping4 2-/SiO2-TiO20.65 portion of 4-hydroxypiperidinol oxyradical, and the reaction temperature is adjusted to 130 ℃ for 3 hours, thus obtaining an esterification product;
(2) and (3) copolymerization reaction: adding 3 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 109 parts by weight of water into a second reaction vessel, uniformly stirring, and uniformly mixing 2 parts by weight of hydrogen peroxide and 20 parts by weight of water in a first dripping device; 0.5 part of 2-hydroxy-2-sulfonic acetic acid, 1.2 parts of 3-mercaptopropionic acid and 20 parts of water are uniformly mixed in a second dripping device; 5 parts of acrylic acid, 1.5 parts of allylthiourea, 4 parts of 3- (2,3, 4-trihydroxyphenyl) -2-acrylic acid 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 mass percent sodium hydroxide to obtain the ester polycarboxylic acid water reducer with the rust-resistant function, wherein the concentration of the ester polycarboxylic acid water reducer is 40%.
Example 3
(1) Preparing an esterification product: 71.13 parts of methacrylic acid and 50 parts of N- [2- (2-hydroxyethoxy) -4-nitrophenyl]Ethanolamine is added into a first reaction containerMixing, adding 0.61 part of supported solid acid catalyst SO under the condition of vacuum pumping4 2-/SiO2-TiO22.42 parts of 4-hydroxypiperidinol oxyl, and adjusting the reaction temperature to 70 ℃ for 5 hours to obtain an esterification product;
(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 monoacrylate with the molecular weight of 1200 and 114 parts by weight of water into a second reaction vessel, uniformly stirring, and uniformly mixing 1 part by weight of ammonium persulfate and 20 parts by weight of water in a first dripping device; 2 parts of 2-hydroxy-2-sulfonic acid acetic acid, 0.5 part of thioglycolic acid and 20 parts of water are uniformly mixed in a second dripping device; uniformly mixing 10 parts of acrylic acid, 0.5 part of allylthiourea, 2 parts of 3- (2,3, 4-trihydroxyphenyl) -2-acrylic acid and 20 parts of water 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 mass percent sodium hydroxide to obtain the ester polycarboxylic acid water reducer with the rust-resistant function, wherein the concentration of the ester polycarboxylic acid water reducer is 40%.
The invention also provides the following comparative examples:
comparative example 1
Selecting a commercially available Point-TS8 type polycarboxylate superplasticizer and Subot
The rust inhibitor for reinforced concrete is compounded 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: according to the parts by weight, 37.18 parts of acrylic acid and 50 parts of N- [2- (2-hydroxyethoxy) -4-nitrophenyl]Ethanolamine is added into a first reaction container for mixing, and 1.74 parts of supported solid acid catalyst SO is added under the condition of vacuum pumping4 2-/SiO2-TiO20.44 portion of methyl hydroquinone, and the reaction temperature is adjusted to 110 ℃, and the reaction is carried out for 4h, obtaining 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 2000-molecular-weight monomethoxy ether-monomethacrylate polyethylene glycol ester and 114 parts by weight of water into a second reaction vessel, uniformly stirring, and uniformly mixing 3 parts by weight of potassium persulfate and 20 parts by weight of water in a first dripping device; 1 part of 2-hydroxy-2-sulfonic acid disodium acetate, 2.5 parts of mercaptoethanol and 20 parts of water are uniformly mixed in a second dripping device; 7 parts of acrylic acid, 2 parts of allyl thiourea, 3 parts of p-hydroxyphenyl acrylic acid 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 mass percent sodium hydroxide to obtain the ester polycarboxylic acid water reducer with the rust-resistant function, wherein the concentration of the ester polycarboxylic acid water reducer is 40%.
Comparative example 3
(1) Preparing an esterification product: adding 37.18 parts by weight of acrylic acid and 50 parts by weight of N-phenyl diethanolamine into a first reaction vessel, mixing, and adding 1.74 parts by weight of supported solid acid catalyst SO under the condition of vacuum pumping4 2-/SiO2-TiO20.44 part of methyl hydroquinone, and adjusting the reaction temperature to 110 ℃ for 4 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 2000-molecular-weight monomethoxy ether-monomethacrylate polyethylene glycol ester and 114 parts by weight of water into a second reaction vessel, uniformly stirring, and uniformly mixing 3 parts by weight of potassium persulfate and 20 parts by weight of water in a first dripping device; 1 part of 2-hydroxy-2-sulfonic acid disodium acetate, 2.5 parts of mercaptoethanol and 20 parts of water are uniformly mixed in a second dripping device; 7 parts of acrylic acid, 2 parts of allylthiourea, 3 parts of 3- (2,3, 4-trihydroxyphenyl) -2-acrylic acid 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 mass percent sodium hydroxide to obtain the ester polycarboxylic acid water reducer with the rust-resistant function, wherein the concentration of the ester polycarboxylic acid water reducer is 40%.
Comparative example 4
(1) Preparing an esterification product: according to the parts by weight, 37.18 parts of acrylic acid and 50 parts of N- [2- (2-hydroxyethoxy) -4-nitrophenyl]Ethanolamine is added into a first reaction container for mixing, and 1.74 parts of supported solid acid catalyst SO is added under the condition of vacuum pumping4 2-/SiO2-TiO20.44 part of methyl hydroquinone, and adjusting the reaction temperature to 110 ℃ for 4 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 2000-molecular-weight monomethoxy ether-monomethacrylate polyethylene glycol ester and 111 parts by weight of water into a second reaction vessel, uniformly stirring, and uniformly mixing 3 parts by weight of potassium persulfate and 20 parts by weight of water in a first dripping device; 1 part of 2-hydroxy-2-sulfonic acid disodium acetate, 2.5 parts of mercaptoethanol and 20 parts of water are uniformly mixed in a second dripping device; 7 parts of acrylic acid, 3 parts of 3- (2,3, 4-trihydroxyphenyl) -2-acrylic acid 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 mass percent sodium hydroxide to obtain the ester polycarboxylic acid water reducer with the rust-resistant function, wherein the concentration of the ester polycarboxylic acid water reducer is 40%.
Comparing the ether polycarboxylic acid water reducing agent with rust-resistant function obtained by synthesis in examples 1-3 with the cement and concrete used in comparative examples 1-4, adopting Fujian cement, the mixing amount of the water reducing agent in examples 1-3 is 0.15% (broken solid part) of the cementing material, the mixing amount of the water reducing agent in comparative examples 2-4 is 0.2% (broken solid part) of the cementing material, and the admixture in comparative example 1 is mixedThe amount is referred to a specific compound formula. The fluidity of the cement paste is tested according to GB/T8077-2The average grain diameter is 1.52 mu m, the montmorillonite is added into the cement as an external additive, the mixing amount is 1 percent, and the result of slurry purification is shown in Table 1. The concrete performance test is carried out according to GB 8076 + 2008 concrete admixture, slump, expansion degree and the like, wherein sand is river sand produced by mansion doors (fineness modulus is 2.6-2.9, mud content is 10%), and the concrete performance is detected according to GB/T31296-2014 concrete corrosion and rust inhibitor. The concrete mixing proportion is as follows: cement 360kg/m3803kg/m of sand3982kg/m stone3The initial slump was controlled to 190. + -. 10mm, and the concrete test results are shown in Table 2.
TABLE 1 Net paste Performance data
Table 2 concrete performance data
As can be seen from the results of the clean slurry performance test in Table 1 and the concrete test in Table 2, the performance of the examples is superior to that of the comparative example, and the results of the comparative example 1 show that compared with the mode of compounding the existing water reducing agent with the rust inhibitor, the ester polycarboxylic acid water reducing agent with the rust inhibiting function provided by the invention has better workability, not only has good rust inhibiting performance, but also has the effect of highly dispersing cement particles and better slump retaining performance under the condition of lower mixing amount;
compared with the prior rust-resistant functional monomer and polyhydroxy monomer of other types, the rust-resistant functional monomer A and the unsaturated polyhydroxy monomer have better rust resistance, better water reducing and slump retaining effects; the unsaturated polyhydroxy monomer is introduced to enable the polycarboxylic acid water reducing agent to resist clay adsorption, and the water reducing and slump retaining performance of the concrete is improved;
the combination of comparative example 4 shows that the addition of the rust-resistant functional monomer B further improves the rust-resistant function of the prepared polycarboxylic acid water reducing agent.
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 (12)
1. An ester polycarboxylic acid water reducing agent with a rust-resistant function is characterized by being prepared by copolymerization of an esterification product, an ester macromonomer, acrylic acid, an unsaturated polyhydroxy monomer and a rust-resistant functional monomer B with double bonds, amino groups and sulfur bonds;
the esterification product is prepared by esterification reaction of a rust-resistant functional monomer A with a benzene ring and a hydroxyl group and an unsaturated acid.
2. The ester-based polycarboxylic acid water reducing agent having a rust-inhibiting function according to claim 1, characterized in that: the unsaturated polyhydroxy monomer is 3- (2,3, 4-trihydroxyphenyl) -2-acrylic acid.
3. The ester-based polycarboxylic acid water reducing agent having a rust-inhibiting function according to claim 1, characterized in that: the rust-resistant functional monomer A is N- [2- (2-hydroxyethoxy) -4-nitrophenyl ] ethanolamine.
4. The ester-based polycarboxylic acid water reducing agent having a rust-inhibiting function according to claim 1, characterized in that: the unsaturated acid is one of acrylic acid and methacrylic acid.
5. The ester-based polycarboxylic acid water reducing agent having a rust-inhibiting function according to claim 1, characterized in that: the mole ratio of the rust-resistant functional monomer A to the unsaturated acid is 1: 1-4.
6. The ester-based polycarboxylic acid water reducing agent having a rust-inhibiting function 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.
7. The ester-based polycarboxylic acid water reducing agent having a rust-inhibiting function according to claim 1, characterized in that: the rust-resistant functional monomer B is allyl thiourea.
8. The ester-based polycarboxylic acid water reducing agent having a rust-inhibiting function according to claim 1, characterized in that: 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 1200-3000.
9. The ester-based polycarboxylic acid water reducing agent having a rust-inhibiting function according to claim 1, characterized in that: 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.
10. The ester-based polycarboxylic acid water reducing agent having a rust-inhibiting function according to claim 9, characterized in that: the chain transfer agent is thioglycolic acid, mercaptoethanol, 3-mercaptopropionic acid, thioglycerol, isooctyl 3-mercaptopropionate and trisodium phosphate;
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.
11. The ester-based polycarboxylic acid water reducing agent having a rust-inhibiting function according to claim 1, characterized in that: the mass ratio of the esterification product to the ester macromonomer, the acrylic acid to the rust-resistant functional monomer B to the unsaturated polyhydroxy monomer is 2-5: 100: 5-10: 0.5-2: 2-4.
12. A method for preparing an ester type polycarboxylic acid water reducing agent with rust-resistant function according to any one of claims 1 to 11,
and (3) carrying out copolymerization reaction on the esterification product, the ester macromonomer, acrylic acid, the unsaturated polyhydroxy monomer and the rust-resistant functional monomer B to obtain the ester polycarboxylic acid water reducer with the rust-resistant function.
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| CN114133467A (en) * | 2021-12-16 | 2022-03-04 | 科之杰新材料集团浙江有限公司 | Unsaturated esterified monomer and ester low-bleeding polycarboxylate superplasticizer and preparation method thereof |
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| CN114133467A (en) * | 2021-12-16 | 2022-03-04 | 科之杰新材料集团浙江有限公司 | Unsaturated esterified monomer and ester low-bleeding polycarboxylate superplasticizer and preparation method thereof |
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