CN114213602A - Viscosity reduction type water reducer and preparation method thereof - Google Patents

Viscosity reduction type water reducer and preparation method thereof Download PDF

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CN114213602A
CN114213602A CN202111641745.2A CN202111641745A CN114213602A CN 114213602 A CN114213602 A CN 114213602A CN 202111641745 A CN202111641745 A CN 202111641745A CN 114213602 A CN114213602 A CN 114213602A
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parts
viscosity
water reducer
molecular weight
acid
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CN114213602B (en
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钟丽娜
王昭鹏
林泽宇
方云辉
郭元强
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Kezhijie New Material Group Fujian Co ltd
Kezhijie New Material Group Co Ltd
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Kezhijie New Material Group Fujian Co ltd
Kezhijie New Material Group Co Ltd
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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
    • 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
    • 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
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
    • Y02W30/00—Technologies for solid waste management
    • Y02W30/50—Reuse, recycling or recovery technologies
    • Y02W30/91—Use of waste materials as fillers for mortars or concrete

Abstract

The invention relates to a viscosity reduction type water reducer, which comprises the following raw materials in parts by weight: 100-200 parts of low molecular weight polyether macromonomer; 1-10 parts of a hydrophobic functional monomer; 5-30 parts of unsaturated acid; 1-10 parts of unsaturated ester; 0.5-8 parts of an initiator; and water. According to the invention, the low molecular weight polyether macromonomer and the hydrophobic functional monomer are introduced for copolymerization, and the prepared viscosity reduction type water reducer can release more free water while maintaining the dispersion function, so that the fluidity of concrete is increased, and a good viscosity reduction effect is achieved.

Description

Viscosity reduction type water reducer and preparation method thereof
Technical Field
The invention relates to the technical field of building additives, in particular to a viscosity reduction type water reducer and a preparation method thereof.
Background
The polycarboxylic acid high-performance water reducing agent has the advantages of low mixing amount, high water reducing rate, good collapse protection performance, strong molecular structure adjustability and the like, and becomes the key point of research and development in the field of concrete water reducing agents at home and abroad.
The application of modern high-strength concrete is spread in various civil engineering fields such as bridge engineering, house construction engineering, port ocean engineering, underground engineering and the like. The improvement of the concrete strength is mainly realized by reducing the water-cement ratio, which leads to the increase of the concrete viscosity, thereby causing a series of construction problems of concrete stirring, transportation, pumping and the like, and limiting the popularization and application of high-strength and ultrahigh-strength concrete to a great extent.
Disclosure of Invention
Based on the viscosity-reducing water reducer, the viscosity of concrete can be reduced, and the fluidity of concrete can be improved.
The viscosity reduction type water reducer comprises the following raw materials in parts by weight:
Figure BDA0003442705970000011
the molecular weight of the low molecular weight polyether macromonomer is 500-1500.
Preferably, the initiator comprises, in parts by weight:
0.5-3 parts of an oxidant;
1-6 parts of a reducing agent.
Preferably, the preparation raw materials of the viscosity-reducing water reducer further comprise, by weight:
2-8 parts of a chain transfer agent and carboxyphosphoric acid;
the molar ratio of the polyether macromonomer to the carboxyphosphoric acid is (1.0-1.2): 1.
Preferably, the unsaturated acid includes at least one of acrylic acid and methacrylic acid.
Preferably, the unsaturated ester comprises at least one of vinyl acetate, glycidyl methacrylate, hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxyethyl methacrylate and hydroxypropyl methacrylate.
The invention also provides a preparation method of the viscosity reduction type water reducer, which comprises the following steps:
putting 100-200 parts by weight of low molecular weight polyether macromonomer, 1-10 parts by weight of hydrophobic functional monomer, 5-30 parts by weight of unsaturated acid, 1-10 parts by weight of unsaturated ester, 0.5-8 parts by weight of initiator and water into a reactor for copolymerization reaction, and obtaining the viscosity reduction type water reducer after the reaction is finished; the molecular weight of the low molecular weight polyether macromonomer is 500-1500.
Preferably, the preparation method of the viscosity-reducing water reducer comprises the following steps:
putting 100-200 parts by weight of the low molecular weight polyether macromonomer, 1-10 parts by weight of the hydrophobic functional monomer, 2-8 parts by weight of the chain transfer agent and water into a reactor, and stirring and dissolving to obtain a first mixed solution;
dropwise adding 5-30 parts of the mixed solution of the unsaturated acid and the 1-10 parts of the unsaturated ester, 0.5-3 parts of an oxidant and 1-6 parts of a reducing agent into the first mixed solution to perform copolymerization reaction, and after the dropwise adding is finished, performing heat preservation reaction to obtain a second mixed solution;
and when the second mixed solution is cooled to room temperature, adjusting the pH of the second mixed solution to 6-7 by using an alkali liquor to obtain the viscosity-reducing water reducer.
Preferably, the method for preparing the low molecular weight polyether macromonomer comprises the steps of:
and (3) placing the low molecular weight polyether macromonomer and the carboxyphosphoric acid in a first reactor for esterification reaction, and obtaining the phosphate-terminated low molecular weight polyether macromonomer after the reaction is finished.
Preferably, the preparation method of the hydrophobic functional monomer comprises the steps of:
and (3) placing unsaturated acid hydroxyalkyl ester and fatty diacid monomethyl ester in a second reactor for esterification reaction, and obtaining the hydrophobic functional monomer after the reaction is finished.
Preferably, the low molecular weight polyether macromonomer comprises at least one of methallyl polyoxyethylene and isopentenyl polyoxyethylene ether.
Compared with the prior art, the invention has the following beneficial effects:
compared with the water reducing agent prepared from the macromolecular macromonomer, the viscosity reduction type water reducing agent prepared by the invention can reduce the molecular weight of the viscosity reduction type water reducing agent while keeping the dispersion function, so that the viscosity reduction type water reducing agent prepared from the low molecular polyether macromonomer has higher freedom of movement in free water than a common water reducing agent, and can rapidly extend the molecular chain of the water reducing agent, thereby rapidly adsorbing and dispersing cement particles, reducing the viscosity of cement paste, increasing the fluidity of concrete, and ensuring that the prepared viscosity reduction type water reducing agent has good viscosity reduction performance.
According to the invention, a hydrophobic functional monomer is introduced for copolymerization, the hydrophobic functional monomer has lipophilicity, the HLB (hydrophile-lyophobic balance) value of the water reducing agent can be reduced, the thickness of a water film layer of cement particles in concrete slurry can be reduced while the adsorption effect between the viscosity reducing agent and the cement particles is maintained, the fluidity of the concrete is further improved, and a good viscosity reduction effect is achieved.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the 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 experimental procedures in the following examples are conventional unless otherwise specified. Test materials, reagents and the like used in the following examples are commercially available unless otherwise specified. In the quantitative tests in the following examples, three replicates were set, and the data are the mean or the mean ± standard deviation of the three replicates.
In addition, "and/or" in the whole text includes three schemes, taking a and/or B as an example, including a technical scheme, and a technical scheme that a and B meet simultaneously; in addition, the technical solutions in the embodiments may be combined with each other, but it must be based on the realization of those skilled in the art that when the technical solutions are contradictory or cannot be considered that such a combination does not exist, and the technical solutions are not within the protection scope of the present invention.
The invention provides a viscosity reduction type water reducer which is prepared from the following raw materials in parts by weight:
Figure BDA0003442705970000031
Figure BDA0003442705970000041
the molecular weight of the low molecular weight polyether macromonomer is 500-1500.
Compared with the water reducing agent prepared from the macromolecular macromonomer, the viscosity reduction type water reducing agent prepared by the invention can reduce the molecular weight of the viscosity reduction type water reducing agent while keeping the dispersion function, so that the viscosity reduction type water reducing agent prepared from the low molecular polyether macromonomer has higher freedom of movement in free water than a common water reducing agent, and can rapidly extend the molecular chain of the water reducing agent, thereby rapidly adsorbing and dispersing cement particles, reducing the viscosity of cement paste, increasing the fluidity of concrete, and ensuring that the prepared viscosity reduction type water reducing agent has good viscosity reduction performance.
According to the invention, a hydrophobic functional monomer is introduced for copolymerization, the hydrophobic functional monomer has lipophilicity, the HLB (hydrophile-lyophobic balance) value of the water reducing agent can be reduced, the thickness of a water film layer of cement particles in concrete slurry can be reduced while the adsorption effect between the viscosity reducing agent and the cement particles is maintained, the fluidity of the concrete is further improved, and a good viscosity reduction effect is achieved.
In some embodiments, the initiator comprises, in parts by weight:
0.5-3 parts of an oxidant;
1-6 parts of a reducing agent.
Specifically, the oxidizing agent and the reducing agent form a redox system as an initiator of the polymerization reaction, and the electron transfer between the oxidizing agent and the reducing agent generates an initiator radical. The initiating speed of the redox system initiator is high.
The oxidant comprises any one of hydrogen peroxide, sodium persulfate and ammonium persulfate.
The reducing agent comprises at least one of ascorbic acid, sodium formaldehyde sulfoxylate, and Bruggolite FF6 (broogman reducer).
In some embodiments, the low molecular weight polyether macromonomer comprises at least one of methallyl polyoxyethylene and isopentenyl polyoxyethylene ether.
In some embodiments, the raw materials for preparing the viscosity-reducing water reducer further comprise, in parts by weight:
2-8 parts of a chain transfer agent and carboxyphosphoric acid;
the molar ratio of the polyether macromonomer to the carboxyphosphoric acid is (1.0-1.2): 1.
Specifically, when the molecular weight of polyether macromonomer is 500-1500, the prepared water reducing agent is small in molecular weight and the same in acid amount, the number of adsorption dispersing groups is small, the adsorption dispersing effect of water reducing agent molecules on cement particles is reduced, therefore, the water reducing agent molecules can be selected to be blocked by carboxyphosphoric acid in side chains, the adsorption effect of phosphate groups in the carboxyphosphoric acid is strong, the phosphate groups are adsorbed on the surfaces of the cement particles in concrete, and the cement particles are dispersed through electrostatic repulsion and steric hindrance, so that a thin and dense water film layer is formed, and the flowability of the concrete is further improved.
It should be noted that the raw material for preparing the viscosity-reducing water reducer may be a low molecular weight polyether macromonomer, or a low molecular weight polyether macromonomer after the low molecular weight polyether macromonomer is capped with carboxyphosphoric acid.
In some embodiments, the carboxyphosphoric acid includes at least one of 2-carboxyphenylphosphoric acid, 3-carboxyphenylphosphoric acid, 4-carboxyphenylphosphoric acid, and 3-phosphorylpropionic acid.
Specifically, the chain transfer agent enables free radicals of the polyether macromonomer, the hydrophobic functional monomer, the unsaturated acid and the unsaturated ester to generate free radical transfer, so that the relative molecular mass of the generated viscosity reduction type water reducer is controlled.
In some embodiments, the chain transfer agent is preferably sodium hypophosphite.
Compared with harmful sulfydryl chain transfer agents, the harmless sodium hypophosphite better meets the requirement of green environmental protection.
In some embodiments, the unsaturated acid comprises at least one of acrylic acid and methacrylic acid.
In some embodiments, the unsaturated ester comprises at least one of vinyl acetate, glycidyl methacrylate, hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxyethyl methacrylate, and hydroxypropyl methacrylate.
The invention also provides a preparation method of the viscosity reduction type water reducer, which comprises the following steps:
putting 100-200 parts by weight of low molecular weight polyether macromonomer, 1-10 parts by weight of hydrophobic functional monomer, 5-30 parts by weight of unsaturated acid, 1-10 parts by weight of unsaturated ester, 0.5-8 parts by weight of initiator and water into a reactor for copolymerization reaction, and obtaining the viscosity reduction type water reducer after the reaction is finished; the molecular weight of the low molecular weight polyether macromonomer is 500-1500.
Specifically, the initiator is firstly decomposed to generate initiator free radicals, and the initiator free radicals are respectively transferred to the low molecular weight polyether macromonomer, the hydrophobic functional monomer, the unsaturated acid and the unsaturated ester to perform polymerization reaction under the environment condition of solvent water, so as to obtain the viscosity-reducing water reducer. The viscosity-reducing water reducer is added into concrete, and ester groups in low-molecular-weight polyether macromonomer and unsaturated ester can be hydrolyzed to release functional groups (hydroxyl, phosphate and carboxyl) in the hydration process of cement in the concrete, so that the viscosity-reducing water reducer has good dispersion retentivity, and the prepared viscosity-reducing water reducer has good water reducing performance.
In some embodiments, the method for preparing the viscosity-reducing water reducer comprises the steps of:
s100, placing 100-200 parts by weight of low molecular weight polyether macromonomer, 1-10 parts by weight of hydrophobic functional monomer, 2-8 parts by weight of chain transfer agent and water in a reactor, and stirring and dissolving to obtain a first mixed solution.
Specifically, when the molecular weight of the polyether macromonomer is 500-1500, the prepared water reducing agent is small in molecular weight, the number of adsorption dispersing groups is small, and the adsorption dispersing effect of water reducing agent molecules on cement particles is reduced, so that the side chain of the water reducing agent molecules can be blocked by using carboxyphosphoric acid, the adsorption effect of phosphate groups in the carboxyphosphoric acid is strong, the phosphate groups are adsorbed on the surfaces of the cement particles in concrete, and the cement particles are dispersed through electrostatic repulsion and steric hindrance effects to form a thin and dense water film layer, so that the fluidity of the concrete is improved.
In some embodiments, the step of capping the low molecular weight polyether macromonomer with carboxyphosphoric acid comprises:
and (3) placing the low molecular weight polyether macromonomer and the carboxyphosphoric acid in a first reactor for esterification reaction, and obtaining the phosphate-terminated low molecular weight polyether macromonomer after the reaction is finished.
Specifically, the preparation method of the phosphate-terminated low molecular weight polyether macromonomer comprises the following specific steps:
adding a low molecular weight polyether macromonomer, carboxyphosphoric acid, a first catalyst and a first polymerization inhibitor into a first reactor, and reacting for 6-12 hours at a constant temperature of 110-130 ℃ to obtain the low molecular weight polyether macromonomer.
Specifically, the first catalyst is added to accelerate the esterification reaction between the low molecular weight polyether macromonomer and the carboxyphosphoric acid, and the catalytic effect of the first catalyst is optimal at 110-130 ℃.
The addition of the first polymerization inhibitor can avoid sudden polymerization of the esterification reaction of the polyether macromonomer with low molecular weight and the carboxyphosphoric acid.
In some embodiments, the first reactor is provided with a condensing device to cool the reactants after the esterification reaction of the low molecular weight polyether macromonomer and the carboxyphosphonic acid, so that the reactants can be conveniently used for preparing the viscosity-reducing water reducer subsequently.
In some embodiments, the temperature is reduced to 40 ℃ after the reaction is complete.
In some embodiments, the low molecular weight polyether macromonomer and the carboxyphosphoric acid can be protected with nitrogen to reduce by-products of the esterification reaction of the low molecular weight polyether macromonomer and the carboxyphosphoric acid.
The molar ratio of the low molecular weight polyether macromonomer to the carboxyphosphoric acid is (1.0-1.2): 1.
The dosage of the first catalyst is 0.1-5% of the mass of the low molecular weight polyether macromonomer.
The dosage of the first polymerization inhibitor is 0.01-0.5% of the mass of the low molecular weight polyether macromonomer.
The first catalyst comprises any one of concentrated sulfuric acid, heteropoly acid, stannous oxide and dibutyl tin oxide.
The first polymerization inhibitor comprises any one of p-hydroxyanisole, hydroquinone, p-tert-butyl catechol and phenothiazine.
S200, dropwise adding 5-30 parts of mixed liquid of unsaturated acid and 1-10 parts of unsaturated ester, 0.5-3 parts of oxidant and 1-6 parts of reducing agent into the first mixed liquid to perform copolymerization reaction, and after the dropwise adding is finished, performing heat preservation reaction to obtain a second mixed liquid.
Furthermore, the preferable dropping time of dropping the mixed solution of the unsaturated acid and the unsaturated ester, the oxidizing agent and the reducing agent is 1.5-3 h, the preferable initial dropping temperature of the copolymerization reaction is 20-40 ℃, and the preferable time of the heat preservation reaction is 0.5-1.5 h.
S300, when the second mixed solution is cooled to room temperature, adjusting the pH of the second mixed solution to 6-7 by using an alkali solution to obtain the viscosity reduction type water reducer.
And adding alkali liquor to adjust the pH value of the viscosity-reducing water reducer to 5-7, so that the stability of the viscosity-reducing water reducer can be improved.
The alkali solution is preferably any one of a 30 wt.% sodium hydroxide solution, a 30 wt.% calcium hydroxide solution, and a 30 wt.% barium hydroxide solution.
Specifically, the molecular weight of the low molecular weight polyether macromonomer is 500-1500.
In some embodiments, the method of preparing the hydrophobic functional monomer comprises the steps of:
placing unsaturated acid hydroxyalkyl ester and fatty diacid monomethyl ester in a second reactor for esterification reaction, and obtaining the hydrophobic functional monomer after the reaction is finished.
Specifically, the preparation method of the hydrophobic functional monomer comprises the following specific steps:
and adding unsaturated acid hydroxyalkyl ester, fatty diacid monomethyl ester, a catalyst and a polymerization inhibitor into a second reactor to perform esterification reaction, reacting at a constant temperature of 110-130 ℃ for 6-12 h, and obtaining the hydrophobic functional monomer after the reaction is finished.
In some embodiments, the hydroxyalkyl esters of unsaturated acids include at least one of hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxyethyl methacrylate, hydroxypropyl methacrylate, 3-chloro-2-hydroxypropyl methacrylate, methyl 2- (hydroxymethyl) acrylate, and 2-hydroxypropyl methacrylate.
In some embodiments, the fatty diacid monomethyl ester comprises at least one of 2-nitro-terephthalic acid monomethyl ester, sebacic acid monomethyl ester, dodecanedioic acid monomethyl ester, malonic acid monomethyl ester, β -methyl glutaric acid monomethyl ester, succinic acid monomethyl ester, suberic acid monomethyl ester, azelaic acid hydrogen methyl ester, adipic acid hydrogen methyl ester.
Wherein the molar ratio of the unsaturated acid hydroxyalkyl ester to the fatty diacid monomethyl ester is (1.0-1.2): 1.
Specifically, the second catalyst is added to accelerate the esterification reaction between unsaturated acid hydroxyalkyl ester and fatty diacid monomethyl ester, and the catalytic effect of the second catalyst is optimal at 110-130 ℃.
The addition of the second polymerization inhibitor can avoid the sudden polymerization of the esterification reaction of the unsaturated acid hydroxyalkyl ester and the fatty diacid monomethyl ester.
The dosage of the second catalyst is 0.1-5% of the mass of the unsaturated acid hydroxyalkyl ester.
The dosage of the second polymerization inhibitor is 0.01-0.5% of the mass of the unsaturated acid hydroxyalkyl ester.
The second catalyst comprises any one of concentrated sulfuric acid, heteropoly acid, stannous oxide and dibutyl tin oxide.
The second polymerization inhibitor comprises any one of p-hydroxyanisole, hydroquinone, p-tert-butyl catechol and phenothiazine.
In some embodiments, the temperature is reduced to 40 ℃ after the reaction is complete.
In some embodiments, the molecular weight unsaturated acid hydroxyalkyl ester and fatty diacid monomethyl ester can be protected with nitrogen to reduce the by-products of the esterification reaction of the unsaturated acid hydroxyalkyl ester and fatty diacid monomethyl ester.
Preparation of mono-low molecular weight polyether macromonomer A
1. Preparation of low molecular weight polyether macromonomer a 1:
adding 0.11mol of isopentenyl polyoxyethylene ether-1200, 0.1mol of 3-carboxyphenyl phosphoric acid, 0.5 mass percent of concentrated sulfuric acid and 0.05 mass percent of p-hydroxyanisole into a first reactor provided with a condensing device, keeping the temperature of 120 ℃ for 6 hours under the protection of nitrogen, and cooling to 40 ℃ after the reaction is finished to obtain the low molecular weight polyether macromonomer A1.
2. Preparation of low molecular weight polyether macromonomer a 2:
adding 0.11mol of isopentenyl polyoxyethylene ether-800, 0.1mol of 3-phosphoryl propionic acid, 0.5 mass percent of concentrated sulfuric acid and 0.05 mass percent of tert-butyl catechol into a first reactor provided with a condensing device, keeping the temperature of 120 ℃ for 6 hours under the protection of nitrogen, and cooling to 40 ℃ after the reaction is finished to obtain the low molecular weight polyether macromonomer A2.
3. Preparation of low molecular weight polyether macromonomer a 3:
adding 0.11mol of methyl allyl polyoxyethylene ether-1500, 0.1mol of 2-carboxyphenyl phosphoric acid, 0.4 mass percent of dibutyltin oxide and 0.05 mass percent of phenothiazine into a first reactor provided with a condensing device, keeping the temperature of 120 ℃ for 6 hours under the protection of nitrogen, and cooling to 40 ℃ after the reaction is finished to obtain the low molecular weight polyether macromonomer A3.
Preparation of Di, hydrophobic monomer B
1. Preparation of hydrophobic monomer B1
Adding 0.10mol of monomethyl sebacate, 0.11mol of hydroxyethyl acrylate, 0.5 mass percent of dibutyltin oxide and 0.05 mass percent of phenothiazine into a first reactor provided with a condensing device, keeping the temperature of 120 ℃ for 6 hours under the protection of nitrogen, and cooling to 40 ℃ after the reaction is finished to obtain the hydrophobic monomer B1.
2. Preparation of hydrophobic monomer B2
Adding 0.10mol of monomethyl glutarate, 0.12mol of hydroxyethyl methacrylate, 0.6 mass percent of concentrated sulfuric acid and 0.05 mass percent of phenothiazine into a first reactor provided with a condensing device, keeping the temperature of 120 ℃ for 6h under the protection of nitrogen, and cooling to 40 ℃ after the reaction is finished to obtain the hydrophobic monomer B2.
3. Preparation of hydrophobic monomer B3
Adding 0.10mol of methyl hydrogen adipate, 0.11mol of 3-chloro-2-hydroxypropyl methacrylate, 0.5 mass percent of stannous oxide and 0.05 mass percent of p-tert-butyl catechol into a first reactor provided with a condensing device, keeping the temperature of 120 ℃ for 6 hours under the protection of nitrogen, and cooling to 40 ℃ after the reaction is finished to obtain the hydrophobic monomer B3.
Preparation of viscosity-reducing water reducer
Example 1
200 parts of phosphoric acid-terminated low-molecular-weight ether macromonomer A1, 4 parts of hydrophobic functional monomer B1, 3 parts of sodium hypophosphite and a proper amount of deionized water are placed in a reactor, stirred and dissolved, a mixed solution of 20 parts of acrylic acid and 2 parts of vinyl acetate, 1 part of ascorbic acid solution and 3 parts of hydrogen peroxide solution are dropwise added into the reactor, the temperature is adjusted to 20-40 ℃ for reaction, the dropwise adding time is 1.5-3 h, the temperature is kept for 0.5-1.5 h after the dropwise adding is finished, the temperature is reduced to room temperature after the reaction is finished, and the pH is adjusted to 6-7 by using liquid alkali to obtain the viscosity-reducing water reducer.
Example 2
200 parts of phosphoric acid-terminated low-molecular-weight ether macromonomer A2, 4 parts of hydrophobic functional monomer B2, 3.5 parts of sodium hypophosphite and a proper amount of deionized water are placed in a reactor, stirred and dissolved, a mixed solution of 20 parts of acrylic acid and 2 parts of ethyl acrylate, 1 part of sodium formaldehyde sulfoxylate and 2.5 parts of hydrogen peroxide solution are dropwise added into the reactor, the temperature is adjusted to 20-40 ℃ for reaction, the dropwise adding time is 1.5-3 hours, the temperature is kept for 0.5-1.5 hours after the dropwise adding is finished, the temperature is reduced to room temperature after the reaction is finished, the pH is adjusted to 6-7 by liquid alkali, and the viscosity-reducing water reducer is obtained.
Example 3
200 parts of phosphoric acid-terminated low molecular weight ether macromonomer A3, 4 parts of hydrophobic functional monomer B2, 4 parts of sodium hypophosphite and a proper amount of deionized water are placed in a reactor, stirred and dissolved, a mixed solution of 24 parts of acrylic acid and 2 parts of vinyl acetate, 1 part of Bruggolite FF6 and 2.5 parts of hydrogen peroxide solution are dropwise added into the reactor, the temperature is adjusted to 20-40 ℃ for reaction, the dropwise adding time is 1.5-3 hours, the temperature is kept for 0.5-1.5 hours after the dropwise adding is finished, the temperature is reduced to room temperature after the reaction is finished, the pH is adjusted to 6-7 by liquid alkali, and the viscosity-reducing water reducer is obtained.
Example 4
200 parts of phosphoric acid-terminated low-molecular-weight ether macromonomer A3, 4 parts of hydrophobic functional monomer B3, 4 parts of sodium hypophosphite and a proper amount of deionized water are placed in a reactor, stirred and dissolved, a mixed solution of 24 parts of acrylic acid and 2 parts of glycidyl methacrylate, 1 part of ascorbic acid solution and 2.5 parts of hydrogen peroxide solution are dropwise added into the reactor, the temperature is adjusted to 20-40 ℃ for reaction, the dropwise adding time is 1.5-3 hours, the temperature is kept for 0.5-1.5 hours after the dropwise adding is finished, the temperature is reduced to room temperature after the reaction is finished, and the pH is adjusted to 6-7 by liquid alkali, so that the viscosity-reducing water reducer is obtained.
Comparative example 1
200 parts of isopentenyl polyoxyethylene ether-2400, 4 parts of hydrophobic functional monomer B1, 3 parts of sodium hypophosphite and a proper amount of deionized water are placed in a reactor, stirred and dissolved, a mixed solution of 20 parts of acrylic acid and 2 parts of vinyl acetate, 1 part of ascorbic acid solution and 3 parts of hydrogen peroxide solution are dropwise added into the reactor, the temperature is adjusted to 20-40 ℃ for reaction, the dropwise adding time is 1.5-3 hours, heat preservation is carried out for 0.5-1.5 hours after the dropwise adding is finished, the temperature is reduced to room temperature after the reaction is finished, and the pH is adjusted to 6-7 by liquid caustic soda to obtain the water reducer.
Comparative example 2
200 parts of isopentenyl polyoxyethylene ether-2400, 3 parts of sodium hypophosphite and a proper amount of deionized water are placed in a reactor, stirred and dissolved, a mixed solution of 20 parts of acrylic acid and 2 parts of vinyl acetate, 1 part of ascorbic acid solution and 3 parts of hydrogen peroxide solution are dropwise added into the reactor, the temperature is adjusted to 20-40 ℃ for reaction, the dropwise adding time is 1.5-3 hours, heat preservation is carried out for 0.5-1.5 hours after the dropwise adding is finished, the temperature is reduced to room temperature after the reaction is finished, and the pH is adjusted to 6-7 by liquid alkali, so that the water reducer is obtained.
Comparative example 3
200 parts of methyl allyl polyoxyethylene ether, 4 parts of sodium hypophosphite and a proper amount of deionized water are placed in a reactor, stirred and dissolved, and a mixed solution of 24 parts of acrylic acid and 2 parts of vinyl acetate, 1 part of Bruggolit are dripped into the reactorTMFF6, 2.5 parts of hydrogen peroxide solution, adjusting the temperature to 20-40 ℃ for reaction, wherein the dropping time is 1.5-3 h, preserving the heat for 0.5-1.5 h after the dropping is finished, cooling to room temperature after the reaction is finished, and adjusting the pH to 6-7 by using liquid caustic soda to obtain the water reducer.
GPC (gel permeation chromatography) tests were carried out on the viscosity-reducing water reducers of examples 1 to 4 and the water reducers of comparative examples 1 to 3, and the test results are shown in Table 1.
The mixing amount of the water reducer is adjusted by adopting red lion cement, when the concrete expansion degree is (650 +/-30) mm, the initial and 1h slump, the initial and 1h expansion degree, the 0h inverted slump cylinder emptying time, the compressive strength at each age and other performances of the water reducer with different molecular weights on the concrete are tested according to GB 8076 + 2008 concrete admixture.
The concrete mixing proportion is as follows: 380kg/m cement380kg/m of fly ash350kg/m of mineral powder3750kg/m of sand3980kg/m of stone3145kg/m of water3。
The concrete test results are shown in table 2.
TABLE 1 GPC measurement results
Sample (I) Mn Mw PDI Conversion rate
Comparative example 1 31918 75202 1.89 88.65
Comparative example 2 35912 74461 1.99 87.29
Comparative example 3 31270 62723 2.14 86.77
Example 1 25459 41183 1.91 87.75
Example 2 29270 42723 1.87 88.77
Example 3 22140 39870 1.69 91.28
Example 4 22201 38255 1.73 92.95
TABLE 2 concrete Performance test results
Figure BDA0003442705970000111
Figure BDA0003442705970000121
The results in Table 1 show that the Mn (weight average molecular weight) and Mw (number average molecular weight) of the viscosity reduction type water reducer prepared by the invention are lower than those of the water reducer prepared by using the conventional macromonomer with the molecular weight of 2400, and the viscosity reduction type water reducer with low molecular weight is successfully prepared by the invention.
Compared with the embodiment 1, the phosphoric acid-terminated low-molecular-weight ether macromonomer (isopentenyl polyoxyethylene ether-1200) is replaced by isopentenyl polyoxyethylene ether-2400, and as can be seen from the data of the embodiment 1 and the comparison example 1 in the table 2, the doping amount and the emptying time of the embodiment 1 are both lower than those of the comparison example 1, which indicates that the introduction of the low-molecular-weight ether macromonomer is favorable for improving the fluidity of concrete, so that the prepared viscosity-reducing water reducer has good viscosity-reducing performance.
The results in Table 2 show that the hydrophobic functional monomer is not added in the comparative example 2, the viscosity of the concrete is higher, and the introduction of the hydrophobic monomer is beneficial to improving the viscosity of the slurry.
The mixing amount and the emptying time of the examples 1 to 4 are lower than those of the comparative examples 1 to 3, which shows that the special low-molecular-weight water reducing agent for high-strength concrete prepared by the invention has better dispersibility and dispersion retentivity, and the fluidity of the concrete is greatly improved.
The technical features of the embodiments described above may be arbitrarily combined, and for the sake of brevity, all possible combinations of the technical features in the embodiments described above are not described, but should be considered as being within the scope of the present specification as long as there is no contradiction between the combinations of the technical features.
The above-mentioned embodiments only express several embodiments of the present invention, and the description thereof is more specific and detailed, but not construed as limiting the scope of the invention. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the inventive concept, which falls within the scope of the present invention. Therefore, the protection scope of the present patent shall be subject to the appended claims.

Claims (10)

1. The viscosity reduction type water reducer is characterized by comprising the following raw materials in parts by weight:
Figure FDA0003442705960000011
water;
the molecular weight of the low molecular weight polyether macromonomer is 500-1500.
2. The viscosity-reducing water reducer according to claim 1, wherein the initiator comprises, in parts by weight:
0.5-3 parts of an oxidant;
1-6 parts of a reducing agent.
3. The viscosity-reducing water reducer according to claim 1, wherein the raw materials for preparing the viscosity-reducing water reducer further comprise, in parts by weight:
2-8 parts of a chain transfer agent and carboxyphosphoric acid;
the molar ratio of the low molecular weight polyether macromonomer to the carboxyphosphoric acid is (1.0-1.2): 1.
4. The viscosity-reducing water reducer according to claim 1, wherein the unsaturated acid comprises at least one of acrylic acid and methacrylic acid.
5. The viscosity-reducing water reducer according to claim 1, wherein the unsaturated ester comprises at least one of vinyl acetate, glycidyl methacrylate, hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxyethyl methacrylate and hydroxypropyl methacrylate.
6. A preparation method of a viscosity reduction type water reducer is characterized by comprising the following steps:
putting 100-200 parts by weight of low molecular weight polyether macromonomer, 1-10 parts by weight of hydrophobic functional monomer, 5-30 parts by weight of unsaturated acid, 1-10 parts by weight of unsaturated ester, 0.5-8 parts by weight of initiator and water into a reactor for copolymerization reaction, and obtaining the viscosity reduction type water reducer after the reaction is finished; the molecular weight of the low molecular weight polyether macromonomer is 500-1500.
7. The preparation method of the viscosity-reducing water reducer according to claim 6, comprising the steps of:
putting 100-200 parts by weight of the low molecular weight polyether macromonomer, 1-10 parts by weight of the hydrophobic functional monomer, 2-8 parts by weight of the chain transfer agent and water into a reactor, and stirring and dissolving to obtain a first mixed solution;
dropwise adding 5-30 parts of the mixed solution of the unsaturated acid and the 1-10 parts of the unsaturated ester, 0.5-3 parts of an oxidant and 1-6 parts of a reducing agent into the first mixed solution to perform copolymerization reaction, and after the dropwise adding is finished, performing heat preservation reaction to obtain a second mixed solution;
and when the second mixed solution is cooled to room temperature, adjusting the pH of the second mixed solution to 6-7 by using an alkali liquor to obtain the viscosity-reducing water reducer.
8. The preparation method of the viscosity-reducing water reducer according to claim 6, wherein the preparation method of the low molecular weight polyether macromonomer comprises the steps of:
and (3) placing the low molecular weight polyether macromonomer and the carboxyphosphoric acid in a first reactor for esterification reaction, and obtaining the phosphate-terminated low molecular weight polyether macromonomer after the reaction is finished.
9. The preparation method of the viscosity-reducing water reducer according to claim 6, wherein the preparation method of the hydrophobic functional monomer comprises the steps of:
and (3) placing unsaturated acid hydroxyalkyl ester and fatty diacid monomethyl ester in a second reactor for esterification reaction, and obtaining the hydrophobic functional monomer after the reaction is finished.
10. The preparation method of the viscosity-reducing water reducer according to claim 8, wherein the low-molecular-weight polyether macromonomer comprises at least one of methallyl polyoxyethylene and isopentenyl polyoxyethylene ether.
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