CN114181086A - Esterification product for preparing water reducing agent and preparation method thereof, and high-workability polycarboxylic acid water reducing agent and preparation method thereof - Google Patents
Esterification product for preparing water reducing agent and preparation method thereof, and high-workability polycarboxylic acid water reducing agent and preparation method thereof Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
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- C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
- C07C69/52—Esters of acyclic unsaturated carboxylic acids having the esterified carboxyl group bound to an acyclic carbon atom
- C07C69/533—Monocarboxylic acid esters having only one carbon-to-carbon double bond
- C07C69/54—Acrylic acid esters; Methacrylic acid esters
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- 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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- C07C69/52—Esters of acyclic unsaturated carboxylic acids having the esterified carboxyl group bound to an acyclic carbon atom
- C07C69/604—Polycarboxylic acid esters, the acid moiety containing more than two carboxyl groups
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- 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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- C04B2103/00—Function or property of ingredients for mortars, concrete or artificial stone
- C04B2103/30—Water reducers, plasticisers, air-entrainers, flow improvers
- C04B2103/302—Water reducers
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Abstract
The invention relates to the technical field of concrete admixtures, in particular to an esterification product for preparing a water reducing agent and a preparation method thereof, and a high-workability polycarboxylic acid water reducing agent and a preparation method thereof, wherein the esterification product for preparing the water reducing agent is a mixture prepared by carrying out esterification reaction on excessive unsaturated carboxylic acid and/or unsaturated carboxylic anhydride and phenoxyethanol and/or phenoxyisopropanol on the esterification product, the esterification product for preparing the water reducing agent provided by the invention enables the main chain of the polycarboxylic acid water reducing agent to be provided with phenoxyethanol and/or phenoxyisopropanol, fumarate and maleate structural units, so that the polycarboxylic acid water reducing agent with self-anticorrosion performance is obtained, a small-molecular preservative does not need to be compounded, the problem of uneven distribution caused by poor compatibility of the preservative and the polycarboxylic acid water reducing agent does not exist, and the final product is of a stable high molecular structure, can endure high temperature higher than 50 ℃, and has more excellent high-temperature corrosion resistance.
Description
Technical Field
The invention relates to the technical field of concrete admixtures, in particular to an esterification product for preparing a water reducing agent and a preparation method thereof, and a high workability polycarboxylic acid water reducing agent and a preparation method thereof.
Background
The conventional method for solving the problem of mildew and odor of the polycarboxylate superplasticizer is a compound preservative, and some people also study the anti-corrosion polycarboxylate superplasticizer.
The method for adding the preservative in the compounding process is the method which is the most widely applied in the prior art, but the compounded preservative generally has a small molecular weight, so that on one hand, the problem of nonuniform dispersion in the polycarboxylic acid water reducing agent can exist, and on the other hand, the problem of decomposition failure of the conventional compounded preservative used at present under the environment of higher than 50 ℃ can also exist, so that the application of the preservative is limited to a certain extent.
For example, patent document CN110642996A discloses a self-preservation polycarboxylic acid water reducing agent and a preparation method thereof, but the monomers used for the self-preservation polycarboxylic acid water reducing agent have preservation performance, and the monomers used for the self-preservation polycarboxylic acid water reducing agent are any one or more of polymethacryloxyethyltrimethylammonium chloride, poly [2- (acryloyloxy) ethyl ] trimethylammonium bromide, poly (benzyltrimethylammonium chloride), polyallyltrimethylammonium chloride and poly (3-acrylamidopropyl) trimethylammonium bromide. However, these materials are already polymers, have no polymerization activity, cannot be grafted into the molecular structure of the water reducing agent, and are prone to have the problem of uneven dispersion in the polycarboxylic acid water reducing agent.
Also, for example, patent document No. CN109796561A discloses an aromatic ring polycarboxylic acid water reducing agent mother liquor, a preparation method and an application thereof, the aromatic group conjugated unsaturated carboxylic acid is used as an antiseptic monomer to prepare the polycarboxylic acid water reducing agent with self-antiseptic effect, but the aryl group conjugated unsaturated carboxylic acid has a large steric hindrance during polymerization, which causes a problem of undesirable polymerization effect, and finally affects the performance of the product.
And as disclosed in patent document CN107265907A, an amphoteric antibacterial polycarboxylic acid high-efficiency water reducing agent and a preparation method thereof are disclosed, the amphoteric antibacterial polycarboxylic acid high-efficiency water reducing agent is subjected to copolymerization and then sequentially reacts with unsaturated polyester macromonomer and halogen-terminated polyether, the process is complicated, and the product conversion rate is limited due to the reaction of large molecular weight and macromolecules, so that the product performance is influenced.
Therefore, the development of the water reducing agent which is convenient to produce, high in cost performance and excellent in corrosion prevention effect is very important.
Disclosure of Invention
In order to solve the problem that the performance of the water reducing agent is reduced due to the compounding of the water reducing agent with the preservative in the prior art, the invention provides an esterification product for preparing the water reducing agent, wherein the esterification product is a mixture prepared by carrying out esterification reaction on excessive first unsaturated carboxylic acid and/or unsaturated carboxylic acid anhydride and phenoxyethanol and/or phenoxyisopropanol.
The invention also provides a method for preparing the esterification product for preparing the water reducing agent as described in any one of the above, wherein,
mixing excessive first unsaturated carboxylic acid and/or unsaturated carboxylic anhydride with phenoxyethanol and/or phenoxyisopropanol and a polymerization inhibitor, heating to 70-90 ℃ in an atmosphere of protective gas, adding a catalyst for heat preservation reaction, and cooling to room temperature after the reaction is finished to obtain a mixture, namely the esterification product.
Preferably, the protective gas is nitrogen, the heat preservation reaction time is 1.0-3.0 h, and water is removed by a vacuumizing or nitrogen water carrying method during the heat preservation reaction.
In one embodiment, the total mass of the phenoxyethanol and/or phenoxyisopropanol is M1The total mass of the first unsaturated carboxylic acid and/or unsaturated carboxylic acid anhydride is M2，M1And M2In the range of 1: (1-3).
In one embodiment, the catalyst is at least one of concentrated sulfuric acid, benzenesulfonic acid, p-toluenesulfonic acid, and ethylsulfonic acid; the polymerization inhibitor is at least one of 4-hydroxy-2, 2,6, 6-tetramethylpiperidine-1-oxygen radical, hydroquinone, phenothiazine and p-hydroxyanisole.
In one embodiment, the addition amount of the polymerization inhibitor is 0.2-3.0% of the total mass of the reactants, and the addition amount of the catalyst is 0.03-0.3% of the total mass of the reactants.
The invention provides a high workability polycarboxylate water reducing agent, which further comprises the following components: esterification products, unsaturated ether macromonomers, unsaturated ester macromonomers, anticorrosion functional small monomers, second unsaturated carboxylic acid and/or unsaturated carboxylic anhydride;
wherein the esterification product is a mixture prepared by reacting excessive first unsaturated carboxylic acid and/or unsaturated carboxylic acid anhydride with phenoxyethanol and/or phenoxyisopropanol.
In one embodiment, the molecular weight of the unsaturated ether macromonomer is 600-6000, and the unsaturated ether macromonomer is at least one of 3-methyl-3-butene-1-polyethylene glycol, 2-methylallyl polyethylene glycol, ethylene glycol monovinyl polyethylene glycol ether, and 4-hydroxybutyl vinyl polyoxyethylene ether.
In one embodiment, the unsaturated ester macromonomer is at least one of esterification products of acrylic acid or methacrylic acid and methoxy polyethylene glycol with a molecular weight of 600-2400.
In one embodiment, the small antiseptic functional monomer is at least one of diethyl maleate, monomethyl fumarate, dimethyl maleate, dipropyl maleate, monoethyl fumarate, and dimethyl fumarate.
In one embodiment, the first unsaturated carboxylic acid and/or unsaturated carboxylic acid anhydride, the second unsaturated carboxylic acid and/or unsaturated carboxylic acid anhydride are at least one of acrylic acid, methacrylic acid, and maleic anhydride.
The invention also provides a preparation method of the high workability polycarboxylate superplasticizer as described in any of the above, wherein,
and mixing the esterification product, the unsaturated ether macromonomer, the unsaturated ester macromonomer, the small monomer with the anticorrosion function and the second unsaturated carboxylic acid and/or unsaturated carboxylic acid anhydride, and carrying out polymerization reaction to obtain the high workability polycarboxylic acid water reducing agent.
In one embodiment, the polymerization reaction is carried out in the presence of an initiator and a molecular weight regulator.
In one embodiment, the unsaturated ether macromonomer, the unsaturated ester macromonomer, the esterification product and the small monomer with the anticorrosion function are mixed and dissolved in water, an initiator aqueous solution, a chain transfer agent aqueous solution and a second unsaturated carboxylic acid and/or unsaturated carboxylic acid anhydride aqueous solution are respectively dripped at the temperature of 5-50 ℃, and heat preservation is carried out for 0-2 hours after dripping is finished for 0.5-3.0 hours, so that the high workability polycarboxylic acid water reducing agent is obtained.
In one embodiment, the mass ratio of the unsaturated ether macromonomer, the unsaturated ester macromonomer, the esterification product, the small anti-corrosive monomer, the second unsaturated carboxylic acid and/or the unsaturated carboxylic acid anhydride is in the range of 300: (20-110): (1-10): (1-10): (35-50).
In one embodiment, the amount of the initiator is 0.5 to 3.0 percent of the total mass of the reactants; the dosage of the molecular weight regulator is 0.2-3.0% of the total mass of the reactants.
In one embodiment, the initiator is a redox initiation system consisting of ferrous sulfate heptahydrate, hydrogen peroxide and sodium formaldehyde sulfoxylate, and the molecular weight regulator is sodium hypophosphite.
Based on the above, compared with the prior art, the invention has the following beneficial effects:
according to the esterification product for preparing the water reducing agent, the phenoxy ethanol and/or phenoxy isopropanol are esterified with unsaturated acid (anhydride) to prepare the unsaturated monomer with the structure of phenoxy ethanol and/or phenoxy isopropanol, and the unsaturated monomer participates in the next reaction, so that the main chain of the polycarboxylic acid water reducing agent is provided with structural units of phenoxy ethanol and/or phenoxy isopropanol, fumarate and maleate, and the polycarboxylic acid water reducing agent with the self-corrosion resistance is obtained, a small-molecular preservative does not need to be compounded, the problem of uneven distribution caused by poor compatibility of the preservative and the polycarboxylic acid water reducing agent does not exist, and the final product is of a stable high-molecular structure, can tolerate the high temperature higher than 50 ℃, and has more excellent high-temperature corrosion resistance.
The preparation method of the esterification product for preparing the water reducing agent provided by the invention has the advantages of low cost and simple and convenient operation by utilizing the phenoxy ethanol and/or the phenoxy isopropanol to carry out esterification with the unsaturated carboxylic acid and/or the unsaturated carboxylic acid anhydride to prepare the esterification product.
The invention provides a high workability polycarboxylate water reducer, which is prepared by introducing phenoxyethanol and/or phenoxyisopropanol, fumarate and maleate structural units into a product molecular structure by copolymerizing a monomer with a phenoxyethanol and/or phenoxyisopropanol ester structure with an unsaturated macromonomer, a small monomer with an anticorrosion function and unsaturated carboxylic acid and/or unsaturated carboxylic anhydride, wherein the polycarboxylate water reducer has the anticorrosion performance without compounding a small-molecular preservative, and the prepared product has the high water reducing performance of an ether product and the high workability of the ester product by copolymerizing the ester and the ether macromonomer.
According to the preparation method of the high-workability polycarboxylate superplasticizer, the adopted raw materials are wide in source, low in price, simple in preparation process, short in synthesis time and high in polymerization rate, and the mechanical property and strength of the interior of concrete are improved on the premise of improving the corrosion resistance, so that the cost of the product is more in line with the application requirement of the polycarboxylate superplasticizer.
Additional features and advantages of the invention will be set forth in the description which follows, and in part will be obvious from the description, or may be learned by practice of the invention. The objectives and other advantages of the invention will be realized and attained by the structure particularly pointed out in the written description and claims hereof.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the following will clearly and completely describe the embodiments of the present invention with reference to the technical solutions thereof, and it is obvious that the described embodiments are some embodiments of the present invention, but not all embodiments; the technical features designed in the different embodiments of the present invention described below can be combined with each other as long as they do not conflict with each other; 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.
In the description of the present invention, it is to be noted that all terms (including technical and scientific terms) used herein have the same meaning as commonly understood by one of ordinary skill in the art to which the present invention belongs, and are not to be construed as limiting the present invention; it will be further understood that terms used herein should be interpreted as having a meaning that is consistent with their meaning in the context of this specification and the relevant art and will not be interpreted in an idealized or overly formal sense unless expressly so defined herein.
The invention also provides the following embodiments:
example 1
(1) Preparing an esterification product: mixing 150.00g of acrylic acid, 140.00g of phenoxyethanol and 2.00g of hydroquinone, heating to 90 ℃ under the protection of nitrogen, adding 1.30g of p-toluenesulfonic acid, keeping the temperature for reaction for 2.0h, removing water by vacuumizing or introducing nitrogen to carry water in the reaction period, and cooling to room temperature after the reaction is finished to obtain a mixture, namely an esterification product A-1.
(2) And (3) copolymerization reaction: 300.00g of 2-methallyl polyethylene glycol with the molecular weight of 2400, 100g of esterification product of acrylic acid and methoxy polyethylene glycol with the molecular weight of 1200, 8.00g of esterification product A-1, 3.00g of monomethyl fumarate, 0.08g of ferrous sulfate heptahydrate, 10.00g of sodium hypophosphite and 278.00g of water are added into a reactor, a stirrer is started, after the materials are uniformly mixed, an acrylic acid aqueous solution (45.00 g of acrylic acid and 20.00g of water), a hydrogen peroxide aqueous solution (3.50 g of hydrogen peroxide and 30.00g of water), a rongalite aqueous solution (3.00 g of rongalite and 30.00g of water) are added dropwise, the initial reaction temperature is 30 ℃, the dropwise addition time is 2.5 hours, the material temperature is controlled to be less than or equal to 50 ℃ in the dropwise addition process, and heat preservation is carried out for 1 hour after the dropwise addition is finished, so that the high-workability polycarboxylic acid water reducing agent B-1 is obtained.
Example 2
(1) Preparing an esterification product: mixing 180.00g of methacrylic acid, 140.00g of phenoxyethanol and 2.50g of 4-hydroxy-2, 2,6, 6-tetramethylpiperidine-1-oxygen free radical, heating to 90 ℃ under the protection of nitrogen, adding 1.30g of concentrated sulfuric acid, carrying out heat preservation reaction for 2.5 hours, removing water by vacuumizing or introducing nitrogen and carrying water, and cooling to room temperature after the reaction is finished to obtain a mixture, namely an esterification product A-2.
(2) And (3) copolymerization reaction: 300.00g of 3-methyl-3-butylene-1-polyethylene glycol with the molecular weight of 2400, 30g of esterification product of acrylic acid and methoxy polyethylene glycol with the molecular weight of 1200, 30g of esterification product of methacrylic acid and methoxy polyethylene glycol with the molecular weight of 1200, 4.00g of esterification product A-2, 4.00g of diethyl maleate, 0.09g of ferrous sulfate heptahydrate and 285.00g of water are added into a reactor, a stirrer is started, when the materials are uniformly mixed, dropwise adding acrylic acid aqueous solution (35.00 g of acrylic acid and 20.00g of water), hydrogen peroxide aqueous solution (3.40 g of hydrogen peroxide and 20.00g of water), mercaptopropionic acid aqueous solution (1.40 g of mercaptopropionic acid and 20.00g of water), ascorbic acid aqueous solution (1.60 g of ascorbic acid and 20.00g of water), the initial reaction temperature is 20 ℃, the dropwise adding time is 3.0h, the temperature of the dropwise adding process is controlled to be less than or equal to 45 ℃, and preserving the heat for 1.5h after the dropwise adding is finished to obtain the high workability polycarboxylate superplasticizer B-2.
Example 3
(1) Preparing an esterification product: 100.00g of maleic anhydride, 70.00g of acrylic acid, 150.00g of phenoxy isopropanol, 1.00g of 4-hydroxy-2, 2,6, 6-tetramethylpiperidine-1-oxygen free radical and 1.0g of hydroquinone are mixed, the temperature is raised to 75 ℃ under the protection of nitrogen, 1.30g of p-toluenesulfonic acid is added, the temperature is kept for reaction for 2.5 hours, water is removed by vacuumizing or introducing nitrogen to carry out water, and the temperature is reduced to room temperature after the reaction is finished, so that an esterification product A-3 is obtained.
(2) And (3) copolymerization reaction: adding 300.00g of 4-hydroxybutyl vinyl polyoxyethylene ether with the molecular weight of 3000, 50g of esterification product of acrylic acid and methoxy polyethylene glycol with the molecular weight of 600, 50g of esterification product of acrylic acid and methoxy polyethylene glycol with the molecular weight of 1200, 6.00g of esterification product A-3, 1.00g of monomethyl fumarate, 2.00g of diethyl maleate, 0.09g of ferrous sulfate heptahydrate and 280.00g of water into a reactor, starting a stirrer, uniformly mixing the materials, dropwise adding an acrylic acid aqueous solution (40.00 g of acrylic acid and 20.00g of water), a hydrogen peroxide aqueous solution (3.30 g of hydrogen peroxide and 20.00g of water), a mercaptoethanol aqueous solution (1.20 g of mercaptoethanol and 20.00g of water) and a reducing agent E51 aqueous solution (512.00g of reducing agent and 20.00g of water), starting reaction temperature is 8 ℃, dropwise adding time is 1.2h, controlling the temperature of the materials to be not more than 35 ℃ in the dropwise adding process, and preserving the heat for 0.5h after the dropwise adding is finished to obtain the high workability polycarboxylate superplasticizer B-3.
Example 4
(1) Preparing an esterification product: mixing 90.00g of methacrylic acid, 70.00g of acrylic acid, 70.00g of phenoxyethanol, 80.00g of phenoxyisopropanol, 1.50g of 4-hydroxy-2, 2,6, 6-tetramethylpiperidine-1-oxygen radical and 1.0g of hydroquinone, heating to 85 ℃ under the protection of nitrogen, adding 0.80g of concentrated sulfuric acid and 0.50g of p-toluenesulfonic acid, carrying out heat preservation reaction for 1.5h, removing water by using a vacuum pumping or nitrogen gas introducing water-carrying method during the reaction, and cooling to room temperature after the reaction is finished to obtain a mixture, namely an esterification product A-4;
(2) and (3) copolymerization reaction: 300.00g of ethylene glycol monovinyl polyglycol ether with the molecular weight of 3000, 100g of esterification product of methacrylic acid and methoxy polyglycol with the molecular weight of 1200, 5.00g of esterification product A-4, 2.00g of monomethyl fumarate, 2.00g of diethyl maleate, 0.08g of ferrous sulfate heptahydrate, 8.00g of sodium hypophosphite and 280.00g of water are added into a reactor, a stirrer is started, after the materials are uniformly mixed, dropwise adding acrylic acid aqueous solution (wherein 36.00g of acrylic acid and 20.00g of water), hydrogen peroxide aqueous solution (wherein 3.00g of hydrogen peroxide and 30.00g of water), reducing agent E51 aqueous solution (wherein E512.20g of reducing agent and 30.00g of water), the initial reaction temperature is 10 ℃, the dropwise adding time is 1.0h, the temperature of the dropwise adding process is controlled to be less than or equal to 30 ℃, and after dropwise adding is finished, the temperature is kept for 0.5h, so that the high-workability polycarboxylate B-4 is obtained.
Comparative example 1
300.00g of 2-methallyl polyethylene glycol with the molecular weight of 2400, 100g of esterification product of acrylic acid and methoxy polyethylene glycol with the molecular weight of 1200, 3.00g of monomethyl fumarate, 0.08g of ferrous sulfate heptahydrate, 10.00g of sodium hypophosphite and 278.00g of water are added into a reactor, a stirrer is started, when the materials are uniformly mixed, an acrylic acid aqueous solution (45.00 g of acrylic acid and 20.00g of water), a hydrogen peroxide aqueous solution (3.50 g of hydrogen peroxide and 30.00g of water) and a rongalite aqueous solution (3.00 g of rongalite and 30.00g of water) are added dropwise, the initial reaction temperature is 30 ℃, the dropwise adding time is 2.5 hours, the material temperature is controlled to be less than or equal to 50 ℃ in the dropwise adding process, and the temperature is kept for 1 hour after the dropwise adding is finished, so that a comparative sample C-1 is obtained.
Comparative example 2
300.00g of 2-methallyl polyethylene glycol with the molecular weight of 2400, 100g of esterification product of acrylic acid and methoxy polyethylene glycol with the molecular weight of 1200, 0.08g of ferrous sulfate heptahydrate, 10.00g of sodium hypophosphite and 278.00g of water are added into a reactor, a stirrer is started, after the materials are uniformly mixed, an acrylic acid aqueous solution (wherein 45.00g of acrylic acid and 20.00g of water), a hydrogen peroxide aqueous solution (wherein 3.50g of hydrogen peroxide and 30.00g of water) and a rongalite aqueous solution (wherein 3.00g of rongalite and 30.00g of water) are added dropwise, the initial reaction temperature is 30 ℃, the dropwise addition time is 2.5 hours, the material temperature in the dropwise addition process is controlled to be less than or equal to 50 ℃, and heat preservation is carried out for 1 hour after dropwise addition is finished, so as to obtain a comparative sample C-2.
Comparative example 3
(1) Preparing an esterification product: mixing 180.00g of methacrylic acid, 154.00g of 3-phenoxy-1-propanol and 2.50g of 4-hydroxy-2, 2,6, 6-tetramethylpiperidine-1-oxygen free radical, heating to 90 ℃ under the protection of nitrogen, adding 1.30g of concentrated sulfuric acid, carrying out heat preservation reaction for 2.5 hours, removing water by vacuumizing or introducing nitrogen to carry out water, and cooling to room temperature after the reaction is finished to obtain a mixture, namely an esterification product D-1.
(2) And (3) copolymerization reaction: 300.00g of 3-methyl-3-butylene-1-polyethylene glycol with the molecular weight of 2400, 30g of esterification product of acrylic acid and methoxy polyethylene glycol with the molecular weight of 1200, 30g of esterification product of methacrylic acid and methoxy polyethylene glycol with the molecular weight of 1200, 4.00g of esterification product D-1, 4.00g of diethyl maleate, 0.09g of ferrous sulfate heptahydrate and 285.00g of water are added into a reactor, a stirrer is started, when the materials are uniformly mixed, dropwise adding acrylic acid aqueous solution (35.00 g of acrylic acid and 20.00g of water), hydrogen peroxide aqueous solution (3.40 g of hydrogen peroxide and 20.00g of water), mercaptopropionic acid aqueous solution (1.40 g of mercaptopropionic acid and 20.00g of water), ascorbic acid aqueous solution (1.60 g of ascorbic acid and 20.00g of water), the initial reaction temperature is 20 ℃, the dropwise adding time is 3.0h, the temperature of the dropwise adding process is controlled to be less than or equal to 45 ℃, and preserving the heat for 1.5 hours after the dropwise adding is finished to obtain the high workability polycarboxylate superplasticizer C-3.
Comparative example 4
(1) Preparing an esterification product: 100.00g of maleic anhydride, 70.00g of acrylic acid, 150.00g of phenoxy isopropanol, 1.00g of 4-hydroxy-2, 2,6, 6-tetramethylpiperidine-1-oxygen free radical and 1.0g of hydroquinone are mixed, the temperature is raised to 75 ℃ under the protection of nitrogen, 1.30g of p-toluenesulfonic acid is added, the temperature is kept for reaction for 2.5 hours, water is removed by vacuumizing or introducing nitrogen to carry out water, and the temperature is reduced to room temperature after the reaction is finished, so that an esterification product A-3 is obtained.
(2) And (3) copolymerization reaction: 350g of an esterification product of acrylic acid and methoxypolyethylene glycol having a molecular weight of 600, 50g of an esterification product of acrylic acid and methoxypolyethylene glycol having a molecular weight of 1200, 6.00g of the esterification product A-3, 1.00g of monomethyl fumarate, 2.00g of diethyl maleate, 0.09g of ferrous sulfate heptahydrate, and 280.00g of water were charged into a reactor, starting a stirrer, and after the materials are uniformly mixed, beginning to dropwise add an acrylic acid aqueous solution (wherein 40.00g of acrylic acid and 20.00g of water), a hydrogen peroxide aqueous solution (wherein 3.30g of hydrogen peroxide and 20.00g of water), a mercaptoethanol aqueous solution (wherein 1.20g of mercaptoethanol and 20.00g of water) and a reducing agent E51 aqueous solution (wherein 20.00g of water) at the initial reaction temperature of 8 ℃, dropwise adding time of 1.2h, controlling the material temperature in the dropwise adding process to be less than or equal to 35 ℃, and preserving heat for 0.5h after dropwise adding is finished to obtain the high-workability polycarboxylic acid water reducing agent C-4.
Comparative example 5
(1) Preparing an esterification product: 100.00g of maleic anhydride, 70.00g of acrylic acid, 150.00g of phenoxy isopropanol, 1.00g of 4-hydroxy-2, 2,6, 6-tetramethylpiperidine-1-oxygen free radical and 1.0g of hydroquinone are mixed, the temperature is raised to 75 ℃ under the protection of nitrogen, 1.30g of p-toluenesulfonic acid is added, the temperature is kept for reaction for 2.5 hours, water is removed by vacuumizing or introducing nitrogen to carry out water, and the temperature is reduced to room temperature after the reaction is finished, so that an esterification product A-3 is obtained.
(2) And (3) copolymerization reaction: 350.00g of 4-hydroxybutyl vinyl polyoxyethylene ether having a molecular weight of 3000, 50g of an esterification product of acrylic acid and methoxypolyethylene glycol having a molecular weight of 1200, 6.00g of the esterification product A-3, 1.00g of monomethyl fumarate, 2.00g of diethyl maleate, 0.09g of ferrous sulfate heptahydrate, and 280.00g of water were charged into a reactor, starting a stirrer, and after uniformly mixing the materials, beginning to dropwise add an acrylic acid aqueous solution (wherein 40.00g of acrylic acid and 20.00g of water), a hydrogen peroxide aqueous solution (wherein 3.30g of hydrogen peroxide and 20.00g of water), a mercaptoethanol aqueous solution (wherein 1.20g of mercaptoethanol and 20.00g of water) and a reducing agent E51 aqueous solution (wherein the reducing agent E512.00g and 20.00g of water), wherein the initial reaction temperature is 8 ℃, the dropwise adding time is 1.2h, the temperature of the materials in the dropwise adding process is controlled to be less than or equal to 35 ℃, and after the dropwise adding is finished, preserving heat for 0.5h to obtain the high-workability polycarboxylic acid water reducing agent C-5.
The grade and other technical indexes of the raw materials adopted in the preparation method, the examples and the comparative examples can be selected according to the prior art, and if the technical indexes are specified in the invention, the technical indexes are selected within the range specified in the invention, so that the technical effect of the invention is not influenced.
1. Testing of concrete Properties
Concrete performance tests are carried out on the water reducing agent samples prepared in the examples and the comparative examples according to GB/T8076-2008, wherein the bending and fixing mixing amount is 0.20%, and the test results are shown in Table 1:
TABLE 1 concrete test results
As can be seen from the test results in Table 1, the performance tests of the examples are overall better than those of the comparative examples, and as shown by the results of the comparison between the example 1 and the comparative example 1, the water reduction rate and the compressive strength ratios of 3d, 7d and 28d of the esterification product A-1 in the example 1 are slightly reduced after the esterification product A-1 is removed, while the products synthesized according to the technical scheme of the patent have higher water reduction rate and compressive strength ratios of 3d, 7d and 28 d. But comparative example 5 synthesized using ether macromonomer alone is slightly inferior in concrete workability compared to examples 1 to 4.
2. Test of Corrosion resistance
Diluting the high workability polycarboxylate water reducer samples prepared in the examples and the comparative samples prepared in the comparative examples to be 15% in concentration, adding 1% of white sugar and 2% of sodium gluconate to compound to obtain final water reducer finished products, placing 300g of each finished product sample in an open glass container with the same volume of 500ml, heating to 50 ℃ for 12 hours, placing in a 30 ℃ thermostat, placing for 15 days (d), 30d, 60d, 90d, 120d and 180d, and observing the state of the sample (whether peculiar smell, turbidity or mildew exists) at corresponding time to compare the corrosion resistance of the samples, wherein the specific test results are shown in table 2.
Table 2 corrosion resistance test results
As can be seen from the test results in table 2, comparative example 2 has started to show off-flavor and mold growth at 30 days, comparative example 1 to which monomethyl fumarate was added during copolymerization has a slightly better preservative effect than comparative example 2, but also shows off-flavor at 120 days and off-flavor and mold growth at 180 days, comparative example 3 to which phenoxyethanol and/or phenoxyisopropanol were replaced with 3-phenoxy-1-propanol also shows off-flavor at 120 days and off-flavor and mold growth at 180 days, indicating that phenoxyethanol and/or phenoxyisopropanol are significantly superior to 3-phenoxy-1-propanol in preservative effect even though they are both phenoxyethanol;
in addition, the test results of comparative example 4 illustrate the fact that the use of the ester macromonomer alone also causes off-flavor at a later stage. Therefore, compared with the comparative example, the anticorrosive high-efficiency polycarboxylic acid water reducing agent prepared in the embodiments 1 to 4 of the invention has obviously better anticorrosive effect.
In addition, it will be appreciated by those skilled in the art that, although there may be many problems with the prior art, each embodiment or aspect of the present invention may be improved only in one or several respects, without necessarily simultaneously solving all the technical problems listed in the prior art or in the background. It will be understood by those skilled in the art that nothing in a claim should be taken as a limitation on that claim.
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 (10)
1. An esterification product for preparing a water reducing agent is characterized in that: the esterification product is a mixture prepared by reacting excessive first unsaturated carboxylic acid and/or unsaturated carboxylic acid anhydride with phenoxyethanol and/or phenoxyisopropanol.
2. A method for preparing an esterification product for use in the preparation of a water reducing agent according to claim 1, characterized by:
mixing excessive first unsaturated carboxylic acid and/or unsaturated carboxylic anhydride, phenoxyethanol and/or phenoxyisopropanol and a polymerization inhibitor, heating to 70-90 ℃ in an atmosphere of protective gas, adding a catalyst for heat preservation reaction, and cooling to room temperature after the reaction is finished to obtain a mixture, namely the esterification product.
3. The method for preparing an esterification product for use in the preparation of a water reducing agent according to claim 2, wherein: the total mass of the phenoxyethanol and/or phenoxyisopropanol is M1The total mass of the first unsaturated carboxylic acid and/or unsaturated carboxylic acid anhydride is M2，M1And M2In the range of 1: (1-3).
4. A high workability polycarboxylate superplasticizer is characterized in that: comprises the following components: esterification products, unsaturated ether macromonomers, unsaturated ester macromonomers, anticorrosion functional small monomers, second unsaturated carboxylic acid and/or unsaturated carboxylic anhydride;
wherein the esterification product is a mixture prepared by reacting excessive first unsaturated carboxylic acid and/or unsaturated carboxylic acid anhydride with phenoxyethanol and/or phenoxyisopropanol.
5. The high workability polycarboxylic acid water reducing agent according to claim 4, characterized in that: the molecular weight of the unsaturated ether macromonomer is 600-6000, and the unsaturated ether macromonomer is at least one of 3-methyl-3-butylene-1-polyethylene glycol, 2-methylallyl polyethylene glycol, ethylene glycol monovinyl polyethylene glycol ether and 4-hydroxybutyl vinyl polyoxyethylene ether.
6. The high workability polycarboxylic acid water reducing agent according to claim 4, characterized in that: the unsaturated ester macromonomer is at least one of esterification products of acrylic acid or methacrylic acid and methoxy polyethylene glycol with the molecular weight of 600-2400.
7. The high workability polycarboxylic acid water reducing agent according to claim 4, characterized in that: the small monomer with the anticorrosion function is at least one of diethyl maleate, monomethyl fumarate, dimethyl maleate, dipropyl maleate, monoethyl fumarate and dimethyl fumarate.
8. The high workability polycarboxylic acid water reducing agent according to claim 5, characterized in that: the first unsaturated carboxylic acid and/or unsaturated carboxylic acid anhydride and the second unsaturated carboxylic acid and/or unsaturated carboxylic acid anhydride are at least one of acrylic acid, methacrylic acid and maleic anhydride respectively.
9. A preparation method of the high workability polycarboxylate superplasticizer according to any one of claims 5 to 8 is characterized by comprising the following steps:
and mixing the esterification product, the unsaturated ether macromonomer, the unsaturated ester macromonomer, the small monomer with the anticorrosion function, the unsaturated carboxylic acid and/or the unsaturated carboxylic acid anhydride, and carrying out polymerization reaction to obtain the high-workability polycarboxylic acid water reducing agent.
10. The method for preparing the high workability polycarboxylic acid water reducing agent according to claim 9, characterized in that: the mass ratio range of the unsaturated ether macromonomer, the unsaturated ester macromonomer, the esterification product, the anti-corrosion small monomer, the second unsaturated carboxylic acid and/or the unsaturated carboxylic acid anhydride is 300: (20-110): (1-10): (1-10): (35-50).
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| WO2024085392A1 (en) * | 2022-10-21 | 2024-04-25 | 주식회사 실크로드시앤티 | Concrete additive comprising polycarboxylate ether-based copolymer compound prepared by reaction of different macromonomers and concrete chemical admixture comprising same |
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| GB1008959A (en) * | 1961-05-16 | 1965-11-03 | Beck & Co Gmbh Dr | Method of producing unsaturated polyester resins |
| CN111378077A (en) * | 2018-12-29 | 2020-07-07 | 江苏苏博特新材料股份有限公司 | Low-temperature-sensitivity polycarboxylic acid superplasticizer and preparation method thereof |
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