CN112300339B - Modified ether polycarboxylic acid water reducing agent and preparation method thereof - Google Patents
Modified ether polycarboxylic acid water reducing agent and preparation method thereof Download PDFInfo
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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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- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
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- C04B24/00—Use of organic materials as active ingredients for mortars, concrete or artificial stone, e.g. plasticisers
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- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
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Abstract
The invention discloses a modified ether polycarboxylic acid water reducing agent and a preparation method thereof, wherein the method comprises the following steps: providing reactants comprising an unsaturated ether macromonomer, a diketo group-containing unsaturated first compound, a polyhedral oligomeric silsesquioxane group-containing unsaturated ester second compound, and an unsaturated carboxylic acid and/or an unsaturated carboxylic acid anhydride; and carrying out polymerization reaction on the reactants to generate the modified ether polycarboxylic acid water reducing agent. Through the mode, the modified ether polycarboxylate superplasticizer with the bleeding resistance effect and the enhancement effect can be obtained.
Description
Technical Field
The invention relates to the technical field of building materials, in particular to a modified ether polycarboxylic acid water reducing agent and a preparation method thereof.
Background
The polycarboxylate superplasticizer is the most main additive variety of the ready-mixed concrete due to excellent performance and environmental protection. In recent years, premixed concrete is developed very rapidly, the dosage of the polycarboxylate superplasticizer is increased, but new performance requirements brought by the technical improvement of premixed concrete cannot be met.
With the acceleration of urbanization process and the rise of landmark buildings, high-rise buildings attract more and more attention and attention of people, and ultra-high-rise pumped concrete is an indispensable material in the high-rise buildings. Because of the gradual shortage of natural river sand resources, desalinized sea sand, machine-made sand and the like are used for replacing natural river sand in recent years, and the desalinized sea sand can wash off relatively fine components in the sand in the process of water washing desalinization, so that concrete produced by using the desalinized sea sand is easy to isolate and bleed. In addition, in the production process of high-strength and ultra-high-strength concrete, the strength of the concrete is expected to be further improved by adding the admixture.
However, the current polycarboxylic acid water reducing agents have failed to meet the above requirements.
Disclosure of Invention
The invention mainly solves the technical problem of providing a modified ether polycarboxylate superplasticizer and a preparation method thereof, and the modified ether polycarboxylate superplasticizer can obtain an anti-bleeding effect and an enhancement effect.
In order to solve the technical problems, the invention adopts a technical scheme that: provides a modified ether polycarboxylic acid water reducing agent, the molecular main chain of the modified ether polycarboxylic acid water reducing agent is linked with cage type silsesquioxane and diketone.
In order to solve the technical problem, the invention adopts another technical scheme that: the preparation method of the modified ether polycarboxylate superplasticizer comprises the following steps: providing reactants comprising an unsaturated ether macromonomer, a diketo group-containing unsaturated first compound, a polyhedral oligomeric silsesquioxane group-containing unsaturated ester second compound, and an unsaturated carboxylic acid and/or an unsaturated carboxylic acid anhydride; and carrying out polymerization reaction on the reactants to generate the modified ether polycarboxylic acid water reducing agent.
Wherein the step of carrying out polymerization reaction on the reactants to generate the modified ether polycarboxylic acid water reducer comprises the following steps: the reactants are subjected to polymerization reaction under the action of an initiator and a molecular weight regulator to generate a modified ether polycarboxylic acid water reducer; wherein the method further comprises: and adjusting the pH value of the modified ether polycarboxylic acid water reducer to 5-7.
Wherein the modified ether polycarboxylic acid water reducing agent is prepared by carrying out polymerization reaction on the reactants under the action of an initiator and a molecular weight regulator, and comprises the following components: providing an aqueous solution of the unsaturated ether macromonomer, adding the first compound and the second compound under the condition of a preset reaction temperature range, and uniformly dispersing the first compound and the second compound within a preset rotation speed range to obtain a first mixed reaction system; and (3) dropwise adding an unsaturated carboxylic acid and/or unsaturated carboxylic anhydride aqueous solution, an initiator aqueous solution and a molecular weight regulator aqueous solution into the first mixed reaction system, and keeping the temperature for a preset time range after the dropwise adding is finished to generate the modified ether polycarboxylate superplasticizer.
Wherein the predetermined reaction temperature range is 0-90 ℃; the predetermined rotating speed range is 320-480 r/min; the dripping time range is 0.2-6 h; the preset time range of heat preservation is 0-3 h; wherein a molar ratio of the unsaturated ether macromonomer, the first compound, the second compound, the unsaturated carboxylic acid and/or unsaturated carboxylic acid anhydride is in a range of 5: (2-3): (1-2): (5-20); wherein the using amount of the initiator is 0.5-3.0% 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.
Wherein the first compound has a structural formula:
wherein R is1Is H or CH3，R2Is empty or alkyl of 1-4 carbons, R3Is alkyl of 1 to 4 carbons, R4Is alkyl of 1-4 carbons.
Wherein the structural formula of the second compound is:
wherein R is5Is alkyl of 1-4 carbons or carboxyl of 1-4 carbons, R6Is alkyl of 1-4 carbons.
Wherein the molecular weight of the unsaturated ether macromonomer is 600-5000, and the unsaturated ether macromonomer is at least one of 4-hydroxybutyl vinyl polyoxyethylene ether, allyl polyethylene glycol, 3-methyl-3-butylene-1-polyethylene glycol and 2-methylallyl polyethylene glycol; wherein the unsaturated carboxylic acid and/or unsaturated carboxylic acid anhydride is at least one of acrylic acid, methacrylic acid and maleic anhydride.
Wherein the initiator is at least one of a water-soluble redox initiation system, a water-soluble peroxide initiator and a water-soluble azo initiator.
Wherein the molecular weight regulator is at least one of thioglycolic acid, mercaptopropionic acid, mercaptoethanol, isopropanol and sodium hypophosphite.
The invention has the beneficial effects that: different from the situation of the prior art, the modified ether polycarboxylic acid water reducer is obtained by introducing a cage-type silsesquioxane and diketone structure into a product molecular structure in a way of copolymerizing unsaturated carboxylic acid (anhydride) with a first compound, a second compound and an unsaturated ether macromonomer, and has excellent initial water reducing effect due to the steric hindrance effect of the cage-type silsesquioxane at the initial stage of adding the modified ether polycarboxylic acid water reducer into concrete; the diketone structure in the molecular structure can form a large amount of hydrogen bonds with water molecules in a system, so that the water-resistant paint has an excellent anti-bleeding effect; the introduced cage-type silsesquioxane and the main chain of the product molecule are linked through ester groups, the ester groups can be gradually hydrolyzed under the concrete alkaline condition, so that the nano-scale cage-type silsesquioxane and the carboxylic acid groups with the water reducing effect are released, the nano-scale cage-type silsesquioxane can be filled into gaps in the concrete to improve the strength of the concrete, and the released carboxylic acid groups provide certain slump retaining capability.
Drawings
In order to more clearly illustrate the technical solutions in the embodiments of the present application, the drawings needed to be used in the description of the embodiments are briefly introduced below, and it is obvious that the drawings in the following description are only some embodiments of the present application, and it is obvious for those skilled in the art to obtain other drawings based on these drawings without creative efforts. Wherein:
FIG. 1 is a schematic flow chart of an embodiment of the preparation method of the modified ether polycarboxylic acid water reducing agent of the invention;
FIG. 2 is a schematic flow chart of another embodiment of the preparation method of the modified ether type polycarboxylate superplasticizer of the invention;
FIG. 3 is a schematic flow chart of a further embodiment of the preparation method of the modified ether polycarboxylic acid water reducing agent of the invention;
FIG. 4 is a schematic flow chart of a further embodiment of the preparation method of the modified ether polycarboxylic acid water reducing agent of the invention.
Detailed Description
The technical solutions in the embodiments of the present application will be clearly and completely described below with reference to the drawings in the embodiments of the present application, and it is obvious that the described embodiments are only a part of the embodiments of the present application, and not all 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 application.
Referring to FIG. 1, FIG. 1 is a schematic flow chart of an embodiment of a preparation method of a modified ether polycarboxylic acid water reducing agent of the present invention, and the method comprises:
step S101: providing reactants comprising unsaturated ether macromonomer, unsaturated first compound containing diketone group, unsaturated ester second compound containing polyhedral oligomeric silsesquioxane group, unsaturated carboxylic acid and/or unsaturated carboxylic acid anhydride.
The polycarboxylate water reducing agent is a high molecular polymer with amphiphilic property, and generally adopts an unsaturated macromonomer with a terminal unsaturated bond (such as a carbon-carbon double bond) and an unsaturated carboxylic acid and/or unsaturated carboxylic acid anhydride micromolecule monomer to perform copolymerization reaction under the action of an initiator, wherein the terminal unsaturated group (such as a terminal alkenyl group) of the large monomer and the terminal unsaturated group of the small monomer form a molecular main chain through copolymerization.
In this embodiment, the unsaturated ether macromonomer, i.e., the polycarboxylic acid water reducing agent unsaturated ether macromonomer, is an ether long-chain monomer having an unsaturated bond (the unsaturated bond is usually at the end, and the unsaturated bond is usually a carbon-carbon double bond) and capable of undergoing a polymerization reaction, relative to the unsaturated carboxylic acid and/or unsaturated carboxylic acid anhydride small-molecule monomer.
In one embodiment, the molecular weight of the unsaturated ether macromonomer is 600-5000.
Unsaturated ether macromonomer is a mainstream macromonomer product at present, and the macromonomer is mainly synthesized into polyethylene glycol ether with terminal group double bonds by ethoxylation reaction of micromolecule unsaturated alcohol initiators with different structures. According to the difference of the molecular structure of the initiator, the synthesized unsaturated macromonomers can be divided into three types: vinyl alcohol 3-carbon macromonomer (allyl polyethylene glycol ether-APEG), vinyl alcohol 4-carbon and 5-carbon macromonomer (isobutenyl polyethylene glycol ether-HPEG, isopentenyl polyethylene glycol ether-TPEG), and vinyl ether 2+2 and 2+4 type macromonomer (EPEG, VPEG).
Specifically, the unsaturated ether macromonomer can be at least one of 4-hydroxybutyl vinyl polyoxyethylene ether, allyl polyethylene glycol, 3-methyl-3-butene-1-polyethylene glycol, and 2-methylallyl polyethylene glycol.
Wherein, the unsaturated carboxylic acid and/or the unsaturated carboxylic acid anhydride are unsaturated micromolecule monomers of the polycarboxylate water reducing agent, and in the copolymerization reaction for generating the polycarboxylate water reducing agent, the unsaturated micromolecule monomers can be single unsaturated carboxylic acid, single unsaturated carboxylic acid anhydride or a mixture of the unsaturated carboxylic acid and the unsaturated carboxylic acid anhydride. In one embodiment, the unsaturated carboxylic acid and/or unsaturated carboxylic acid anhydride may be at least one of acrylic acid, methacrylic acid, and maleic anhydride.
The diketone group-containing unsaturated first compound means a compound having a diketone group and an unsaturated bond. The unsaturated bond is used for linking the first compound to the molecular structure of the modified ether polycarboxylic acid water reducer, and the diketone is used for modifying the ether polycarboxylic acid water reducer, so that the modified ether polycarboxylic acid water reducer has a diketone structure which can form a large number of hydrogen bonds with water molecules in a concrete system, and the modified ether polycarboxylic acid water reducer has an excellent anti-bleeding effect.
Wherein the structural formula of the first compound is:
wherein R is1Is H or CH3，R2Is empty or alkyl of 1-4 carbons, R3Is alkyl of 1 to 4 carbons, R4Is alkyl of 1-4 carbons.
The unsaturated ester second compound containing a cage-type silsesquioxane group means a compound having a cage-type silsesquioxane group, an unsaturated bond, and an ester group. The unsaturated bond is used for linking the second compound to the molecular structure of the modified ether polycarboxylic acid water reducing agent, the cage-type silsesquioxane group and the ester group are used for modifying the ether polycarboxylic acid water reducing agent, the modified ether polycarboxylic acid water reducing agent has the cage-type silsesquioxane group and the ester group, and the ester group is gradually hydrolyzed under the concrete alkaline condition, so that the nano-scale cage-type silsesquioxane and the carboxylic acid group with the water reducing effect are released, the nano-scale cage-type silsesquioxane can fill gaps in the concrete, and the strength of the concrete is improved; the released carboxylic acid groups realize certain slow-release slump retaining performance.
Wherein the structural formula of the second compound is:
wherein R is5Is alkyl of 1-4 carbons or alkyl of 1-4 carbonsCarboxy, R6Is alkyl of 1-4 carbons.
Step S102: and (3) carrying out polymerization reaction on the reactants to generate the modified ether polycarboxylic acid water reducing agent.
According to the embodiment of the invention, a cage-type silsesquioxane and diketone structure is introduced into a product molecular structure in a way of copolymerization of unsaturated carboxylic acid (anhydride), a first compound, a second compound and an unsaturated ether macromonomer to obtain a modified ether polycarboxylate water reducer, and the modified ether polycarboxylate water reducer has an excellent initial water reducing effect at the initial stage of adding the modified ether polycarboxylate water reducer into concrete due to the steric hindrance effect of the cage-type silsesquioxane; the diketone structure in the molecular structure can form a large amount of hydrogen bonds with water molecules in a system, so that the water-resistant paint has an excellent anti-bleeding effect; the introduced cage-type silsesquioxane and the main chain of the product molecule are linked through ester groups, the ester groups can be gradually hydrolyzed under the concrete alkaline condition, so that the nano-scale cage-type silsesquioxane and the carboxylic acid groups with the water reducing effect are released, the nano-scale cage-type silsesquioxane can be filled into gaps in the concrete to improve the strength of the concrete, and the released carboxylic acid groups provide certain slump retaining capability.
Referring to fig. 2, step S102 may specifically include: the reactants are polymerized under the action of an initiator and a molecular weight regulator to generate the modified ether polycarboxylic acid water reducer.
The initiator, also called as free radical initiator, refers to a kind of compound which is easy to be decomposed into free radicals (i.e. primary free radicals) by heating, and can be used for initiating free radical polymerization and copolymerization of alkene and diene monomers, and also can be used for crosslinking curing and macromolecule crosslinking reaction of unsaturated polyester. The initiator is widely classified into a peroxide initiator, an azo initiator, a redox initiator and the like, and the peroxide initiator is classified into an organic peroxide initiator and an inorganic peroxide initiator. In one embodiment, the initiator is at least one of a water-soluble redox initiation system, a water-soluble peroxide initiator, and a water-soluble azo initiator.
The molecular weight regulator is a substance capable of controlling the molecular weight of the polymer and reducing the branching of polymer chains, and is characterized by large chain transfer constant, so that the molecular weight of the polymer can be effectively reduced by using a small amount, thereby being beneficial to the post-processing and application of the polymer. It is widely used in radical polymerization, and has many kinds of aliphatic thiols, xanthogen disulfides, polyphenol, sulfur, halides, nitroso compounds, etc. In one embodiment, the molecular weight regulator is at least one of thioglycolic acid, mercaptopropionic acid, mercaptoethanol, isopropanol, and sodium hypophosphite.
Referring to fig. 3, the method further comprises:
step S103: and adjusting the pH value of the modified ether polycarboxylic acid water reducing agent to 5-7.
The pH value of the modified ether polycarboxylate superplasticizer is adjusted to 5-7, so that the corrosion to production equipment due to too low or too low pH value can be avoided, the dangerous hidden danger to production and use personnel can be avoided, and the influence on the product color due to the pH value higher than 7 can be avoided.
Referring to fig. 4, in step S102, the reactants are subjected to a polymerization reaction under the action of the initiator and the molecular weight regulator to generate the modified ether polycarboxylic acid water reducing agent, which may specifically include: substep S1021 and substep S1022.
Substep S1021: providing an aqueous solution of an unsaturated ether macromonomer, adding a first compound and a second compound under the condition of a preset reaction temperature range, and uniformly dispersing the first compound and the second compound in a preset rotating speed range to obtain a first mixed reaction system.
Substep S1022: and (3) dropwise adding an unsaturated carboxylic acid and/or unsaturated carboxylic anhydride aqueous solution, an initiator aqueous solution and a molecular weight regulator aqueous solution into the first mixed reaction system, and keeping the temperature for a preset time range after the dropwise adding is finished to generate the modified ether polycarboxylate superplasticizer.
Wherein the predetermined reaction temperature range is 0-90 ℃, for example: 0 ℃, 30 ℃, 60 ℃, 90 ℃, and the like; the predetermined speed range is 320-: 320r/min, 400r/min, 480r/min, etc.; the dropping time ranges from 0.2 to 6h, for example: 0.2h, 1h, 3h, 5h, 6h, etc.; the predetermined time range of the heat preservation is 0 to 3h, for example: 0h, 1h, 2h, 3h, etc.
Wherein the molar ratio of the unsaturated ether macromonomer, the first compound, the second compound, the unsaturated carboxylic acid and/or the unsaturated carboxylic acid anhydride is within a range of 5: (2-3): (1-2): (5-20), for example: the molar ratio of the unsaturated ether macromonomer, the first compound, the second compound, the unsaturated carboxylic acid and/or the unsaturated carboxylic acid anhydride is 5: 2: 1: 5. or 5: 2.5: 1.5: 12.5, or 5: 3: 2: 20, and so on.
Wherein the amount of the initiator is 0.5-3.0% of the total mass of the reactants, such as: 0.5%, 1.0%, 2.0%, 3.0%, etc.; the molecular weight regulator is used in an amount of 0.2 to 3.0% by mass of the total mass of the reactants, for example: 0.2%, 1.0%, 2.0%, 3.0%, etc.
The invention also provides a modified ether polycarboxylic acid water reducing agent, and the molecular main chain of the modified ether polycarboxylic acid water reducing agent is linked with cage type silsesquioxane and diketone groups.
Specifically, the modified ether polycarboxylic acid water reducing agent of the embodiment of the present invention can be prepared by the above preparation method of the modified ether polycarboxylic acid water reducing agent, and for the detailed description of the relevant contents, refer to the above method section, which is not described in detail herein.
The preparation of the examples of the invention is further illustrated and described below by means of specific examples.
Example 1:
(1) 180.00g of 2-methylallyl polyethylene glycol having a molecular weight of 2400 and 140.00g of water were added to the reactor, the stirrer and the temperature control were switched on, 5.20g of 3-allylpentane-2, 4-dione and 14.00g of MA0701 (MA 0701-AcryloIsobutyl, Hybrid Plastics Inc.) were added until the 2-methylallyl polyethylene glycol had completely dissolved
) Adjusting the rotating speed of the stirrer to 330r/min, and after the 3-allyl pentane-2, 4-dione and MA0701 are uniformly dispersed, dropwise adding an acrylic acid aqueous solution (wherein 15.00g of acrylic acid and 20.00g of water) and a hydrogen peroxide aqueous solution (wherein 2.00g of hydrogen peroxide and 3 g of water)0.00g), ascorbic acid aqueous solution (wherein, ascorbic acid is 0.40g, water is 30.00g), thioglycolic acid aqueous solution (wherein, thioglycolic acid is 1.10g, water is 30.00g), reaction temperature is 40 ℃, dropping time is 3.0h, and heat preservation is carried out for 0.5h after dropping is finished, thus obtaining copolymerization product;
(2) and (2) adjusting the pH of the copolymerization product prepared in the step (1) to 5-7 by using alkali to obtain the modified ether polycarboxylic acid water reducer KZJ-1.
Example 2:
(1) 200.00g of 3-methyl-3-butene-1-polyethyleneglycol having a molecular weight of 2400 and 170.00g of water were added to the reactor, the stirrer and the temperature control device were started, and 6.10g of 3-vinylpentan-2, 4-dione and 18.00gMA0702 (MA 0702-methacryloyl isobutyl from Hybrid Plastics) were added until all the 3-methyl-3-butene-1-polyethyleneglycol had dissolved
) Adjusting the rotating speed of the stirrer to 370r/min, after the 3-vinyl pentane-2, 4-dione and MA0702 are uniformly dispersed, beginning to dropwise add an acrylic acid aqueous solution (wherein, 18.00g of acrylic acid and 20.00g of water), an ammonium persulfate aqueous solution (wherein, 1.60g of ammonium persulfate and 30.00g of water), a sodium hypophosphite aqueous solution (wherein, 2.60g of sodium hypophosphite and 30.00g of water), at the reaction temperature of 60 ℃, dropwise adding time of 3.0h, and preserving heat for 1.0h after dropwise adding is finished to obtain a copolymerization product;
(2) and (2) adjusting the pH of the copolymerization product prepared in the step (1) to 5-7 by using alkali to obtain the modified ether polycarboxylic acid water reducer KZJ-2.
Example 3:
(1) 150.00g of 4-hydroxybutyl vinyl polyoxyethylene ether having a molecular weight of 3000 and 150.00g of water are added to the reactor, the stirrer and the temperature control device are switched on, 4.10g of 3-alkenylbutylpentane-2, 4-dione and 10.00gMA0717 (MA 0717-Methylcryl Ether, Hybrid Plastics Co.) are added after the 4-hydroxybutyl vinyl polyoxyethylene ether has completely dissolved
) Adjusting the rotating speed of the stirrer to 420r/min, and after the 3-alkene butyl pentane-2, 4-diketone and MA0717 are uniformly dispersed, beginning to dropwise add acrylic acid and horseThe method comprises the following steps of (1) preparing a mixed solution of maleic anhydride (wherein 6.00g of acrylic acid, 8.00g of maleic anhydride and 40.00g of water), a hydrogen peroxide aqueous solution (wherein 1.20g of hydrogen peroxide and 20.00g of water), a rongalite aqueous solution (wherein 0.40g of rongalite and 20.00g of water), a ferrous sulfate aqueous solution (wherein 0.05g of ferrous sulfate and 20.00g of water) and a mercaptopropionic acid aqueous solution (wherein 1.20g of mercaptopropionic acid and 20.00g of water), reacting at 10 ℃ for 0.5h, and preserving heat for 1.5h after the dropwise addition is finished to obtain a copolymerization product;
(2) and (2) adjusting the pH of the copolymerization product prepared in the step (1) to 5-7 by using alkali to obtain the modified ether polycarboxylic acid water reducer KZJ-3.
Example 4:
(1) 100.00g of 3-methyl-3-butene-1-polyethyleneglycol having a molecular weight of 2400, 50.00g of 2-methylallyl polyethyleneglycol having a molecular weight of 2400 and 200.00g of water were added to the reactor, the stirrer and the temperature control were started, and 4.50g of 4-allyl-n-heptane-3, 5-dione and 13.00gMA0702 (MA 0702-Methacryloisobutyl, Hybrid Plastics, Inc.) were added until the polyether macromonomer had completely dissolved
) Adjusting the rotating speed of a stirrer to 400r/min, after 4-allyl n-heptane-3, 5-dione and MA0702 are uniformly dispersed, beginning to dropwise add a mixed solution of acrylic acid and methacrylic acid (wherein 14.00g of acrylic acid, 3.00g of methacrylic acid and 40.00g of water), an aqueous solution of azodiisobutyl amidine hydrochloride (wherein 2.00g of azodiisobutyl amidine hydrochloride and 30.00g of water), an aqueous solution of thioglycolic acid (wherein 0.90g of thioglycolic acid and 30.00g of water), at the reaction temperature of 30 ℃, for 3.5 hours, and preserving heat for 0.5 hours after dropwise adding to obtain a copolymerization product;
(2) and (2) adjusting the pH of the copolymerization product prepared in the step (1) to 5-7 by using alkali to obtain the modified ether polycarboxylic acid water reducer KZJ-4.
Example 5:
(1) 200.00g of 2-methylallyl polyethylene glycol with a molecular weight of 2400 and 160.00g of water are added to the reactor, the stirrer and the temperature control device are switched on, 4.40g of 3-allylpentane-2, 4-dione and 2.00g of 3-allylhexane are added until the 2-methylallyl polyethylene glycol is completely dissolvedAlkane-2, 4-dione and 16.00g MA0701 (MA 0701-AcryloIsobutyl from Hybrid Plastics, Inc.)
) Adjusting the rotating speed of a stirrer to 360r/min, after 3-allyl pentane-2, 4-diketone, 3-allyl hexane-2, 4-diketone and MA0701 are uniformly dispersed, beginning to dropwise add an acrylic acid aqueous solution (wherein 16.00g of acrylic acid and 20.00g of water), a hydrogen peroxide aqueous solution (wherein 2.00g of hydrogen peroxide and 20.00g of water), an ascorbic acid aqueous solution (wherein 0.50 g of ascorbic acid and 20.00g of water) and a mercaptopropionic acid aqueous solution (wherein 1.60g of mercaptoacetic acid and 20.00g of water), wherein the reaction temperature is 50 ℃, the dropwise adding time is 2.0h, and after dropwise adding, keeping the temperature for 1.5h to obtain a copolymerization product;
(2) and (2) adjusting the pH of the copolymerization product prepared in the step (1) to 5-7 by using alkali to obtain the modified ether polycarboxylic acid water reducer KZJ-5.
Comparative example 1:
(1) 180.00g of 2-methylallyl polyethylene glycol having a molecular weight of 2400 and 140.00g of water were added to the reactor, starting the stirrer and the temperature control device, adding 5.20g of 3-allylpentane-2, 4-dione when the 2-methylallyl polyethylene glycol is completely dissolved, adjusting the rotating speed of the stirrer to 330r/min, after the 3-allylpentane-2, 4-dione is uniformly dispersed, dropping acrylic acid aqueous solution (wherein 16.08g of acrylic acid and 20.00g of water), hydrogen peroxide aqueous solution (wherein 2.00g of hydrogen peroxide and 30.00g of water), ascorbic acid aqueous solution (wherein 0.40g of ascorbic acid and 30.00g of water) and thioglycolic acid aqueous solution (wherein 1.10g of thioglycolic acid and 30.00g of water) at the reaction temperature of 40 ℃ for 3.0h, and preserving heat for 0.5h after dropping to obtain a copolymerization product;
(2) and (3) adjusting the pH of the copolymerization product prepared in the step (1) to 5-7 by using alkali to obtain a comparison sample PCE-1.
Comparative example 2:
(1) 180.00g of 2-methylallyl polyethylene glycol having a molecular weight of 2400 and 140.00g of water were added to the reactor, the stirrer and the temperature control were switched on, and 14.00g of MA0701 (MA 0701-AcryloIsobutyl from Hybrid Plastics) were added after the 2-methylallyl polyethylene glycol had dissolved completely
) Adjusting the rotating speed of the stirrer to 330r/min, after MA0701 is uniformly dispersed, dropwise adding an acrylic acid aqueous solution (wherein 17.67g of acrylic acid and 20.00g of water), a hydrogen peroxide aqueous solution (wherein 2.00g of hydrogen peroxide and 30.00g of water), an ascorbic acid aqueous solution (wherein 0.40g of ascorbic acid and 30.00g of water), a thioglycolic acid aqueous solution (wherein 1.10g of thioglycolic acid and 30.00g of water), reacting at the temperature of 40 ℃, dropwise adding for 3.0 hours, and preserving heat for 0.5 hour after dropwise adding is finished to obtain a copolymerization product;
(2) and (2) adjusting the pH of the copolymerization product prepared in the step (1) to 5-7 by using alkali to obtain a comparison sample PCE-2.
The ether anti-bleeding type polycarboxylate water reducers prepared in examples 1 to 5 and the polycarboxylate water reducers prepared in comparative examples 1 and 2 were subjected to a performance test according to GB/T8076-2008, wherein the test results are shown in Table 1, wherein the bending and fixing mixing amounts of the polycarboxylate water reducers are 0.20 percent:
TABLE 1 test results for different water reducing agents
The comparison result of the PCE-1 and the KZJ-1 shows that the water reducing rate of the PCE-1 prepared by converting MA0701 in the KZJ-1 into acrylic acid in an equimolar way is lower than that of the KZJ-1, the compressive strength ratio of 1d, 3d, 7d and 28d is also lower than that of the KZJ-1, and the bleeding rate ratio is almost the same as that of the KZJ-1. The comparison result of the PCE-2 and the KZJ-1 shows that the water reducing rate, the 1d, 3d, 7d and 28d compressive strength ratio and the KZJ-1 of the PCE-2 prepared by converting 3-allyl pentane-2, 4-diketone in the KZJ-1 into acrylic acid in the same mole are not different, but the bleeding rate ratio is obviously higher than that of the KZJ-1. In addition, the water reducing rates of KZJ-1 to KZJ-5 are all higher than 45%, the compressive strength ratios at 1d are all higher than 310%, the compressive strength ratios at 3d are all higher than 270%, the compressive strength ratios at 7d are all higher than 240%, the compressive strength ratios at 28d are all higher than 200%, and the bleeding rate ratios are all 0%, which shows that the ether anti-bleeding type polycarboxylate water reducer prepared by the invention has excellent bleeding resistance and reinforcing effects.
The above description is only a preferred embodiment of the present invention, and not intended to limit the scope of the present invention, and all modifications of equivalent structures and equivalent processes, which are made by using the contents of the present specification and the accompanying drawings, or directly or indirectly applied to other related technical fields, are included in the scope of the present invention.
Claims (8)
1. The modified ether polycarboxylic acid water reducing agent is characterized in that raw materials for preparing the modified ether polycarboxylic acid water reducing agent comprise unsaturated first compounds containing diketone groups and unsaturated ester second compounds containing cage-type silsesquioxane groups, the molecular main chain of the modified ether polycarboxylic acid water reducing agent is linked with the cage-type silsesquioxane groups and the diketone groups,
the first compound has the structural formula:
wherein R is1Is H or CH3，R2Is empty or alkyl of 1-4 carbons, R3Is alkyl of 1 to 4 carbons, R4Is alkyl of 1-4 carbons;
the structural formula of the second compound is:
wherein R is5Is alkyl of 1-4 carbons or carboxyl of 1-4 carbons, R6Is alkyl of 1-4 carbons.
2. The preparation method of the modified ether polycarboxylic acid water reducing agent is characterized by comprising the following steps:
providing reactants comprising an unsaturated ether macromonomer, a diketo group-containing unsaturated first compound, a polyhedral oligomeric silsesquioxane group-containing unsaturated ester second compound, and an unsaturated carboxylic acid and/or an unsaturated carboxylic acid anhydride;
carrying out polymerization reaction on the reactants to generate a modified ether polycarboxylic acid water reducing agent;
the first compound has the structural formula:
wherein R is1Is H or CH3，R2Is empty or alkyl of 1-4 carbons, R3Is alkyl of 1 to 4 carbons, R4Is alkyl of 1-4 carbons;
the structural formula of the second compound is:
wherein R is5Is alkyl of 1-4 carbons or carboxyl of 1-4 carbons, R6Is alkyl of 1-4 carbons.
3. The method of claim 2, wherein the polymerizing the reactants to produce the modified ether based polycarboxylic acid water reducer comprises:
the reactants are subjected to polymerization reaction under the action of an initiator and a molecular weight regulator to generate a modified ether polycarboxylic acid water reducer;
wherein the method further comprises:
and adjusting the pH value of the modified ether polycarboxylic acid water reducer to 5-7.
4. The method according to claim 3, wherein the step of polymerizing the reactants under the action of the initiator and the molecular weight regulator to generate the modified ether polycarboxylic acid water reducer comprises the following steps:
providing an aqueous solution of the unsaturated ether macromonomer, adding the first compound and the second compound under the condition of a preset reaction temperature range, and uniformly dispersing the first compound and the second compound within a preset rotation speed range to obtain a first mixed reaction system;
and (3) dropwise adding an unsaturated carboxylic acid and/or unsaturated carboxylic anhydride aqueous solution, an initiator aqueous solution and a molecular weight regulator aqueous solution into the first mixed reaction system, and keeping the temperature for a preset time range after the dropwise adding is finished to generate the modified ether polycarboxylate superplasticizer.
5. The method of claim 4, wherein the predetermined reaction temperature range is 0-90 ℃; the predetermined rotating speed range is 320-480 r/min; the dripping time range is 0.2-6 h; the preset time range of heat preservation is 0-3 h;
wherein a molar ratio of the unsaturated ether macromonomer, the first compound, the second compound, the unsaturated carboxylic acid and/or unsaturated carboxylic acid anhydride is in a range of 5: (2-3): (1-2): (5-20);
wherein the using amount of the initiator is 0.5-3.0% 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.
6. The method as claimed in claim 2, wherein the molecular weight of the unsaturated ether-based macromonomer is 600-5000, and the unsaturated ether-based macromonomer is at least one of 4-hydroxybutyl vinyl polyoxyethylene ether, allyl polyethylene glycol, 3-methyl-3-butene-1-polyethylene glycol, and 2-methylallyl polyethylene glycol;
wherein the unsaturated carboxylic acid and/or unsaturated carboxylic acid anhydride is at least one of acrylic acid, methacrylic acid and maleic anhydride.
7. The method according to claim 3, wherein the initiator is at least one of a water-soluble redox initiation system, a water-soluble peroxide initiator, and a water-soluble azo initiator.
8. The method of claim 3, wherein the molecular weight regulator is at least one of thioglycolic acid, mercaptopropionic acid, mercaptoethanol, isopropanol, and sodium hypophosphite.
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