CN111793216A - Early-strength polycarboxylate water reducing agent and preparation method thereof - Google Patents
Early-strength polycarboxylate water reducing agent and preparation method thereof Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G81/00—Macromolecular compounds obtained by interreacting polymers in the absence of monomers, e.g. block polymers
- C08G81/02—Macromolecular compounds obtained by interreacting polymers in the absence of monomers, e.g. block polymers at least one of the polymers being obtained by reactions involving only carbon-to-carbon unsaturated bonds
- C08G81/024—Block or graft polymers containing sequences of polymers of C08C or C08F and of polymers of C08G
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B24/00—Use of organic materials as active ingredients for mortars, concrete or artificial stone, e.g. plasticisers
- C04B24/24—Macromolecular compounds
- C04B24/28—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
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- 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
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/04—Acids; Metal salts or ammonium salts thereof
- C08F220/06—Acrylic acid; Methacrylic acid; Metal salts or ammonium salts thereof
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
- C08F283/06—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polyethers, polyoxymethylenes or polyacetals
- C08F283/065—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polyethers, polyoxymethylenes or polyacetals on to unsaturated polyethers, polyoxymethylenes or polyacetals
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- C—CHEMISTRY; METALLURGY
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- 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
- C04B2103/0045—Polymers chosen for their physico-chemical characteristics
- C04B2103/0059—Graft (co-)polymers
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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
- 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 discloses an early-strength polycarboxylic acid water reducer and a preparation method thereof, and the early-strength polycarboxylic acid water reducer is prepared by the following steps: (1) carrying out water-phase oxidation-reduction free radical polymerization on an unsaturated acid or derivative monomer thereof and an unsaturated polyether macromonomer or unsaturated ester macromonomer under the combined action of an initiator, a reducing agent and a chain transfer agent to obtain a water reducing agent prepolymerization product; (2) grafting metal-organic framework (MOF) nanoparticles containing amino to the molecular structure of a pre-polymerization product of the water reducing agent, and performing amidation reaction to obtain the early-strength polycarboxylic acid water reducing agent. The polycarboxylic acid water reducer prepared by the method is an early-strength polycarboxylic acid water reducer, can improve the early strength of concrete on the premise of not influencing high water reduction in the initial stage, and has stable product performance.
Description
Technical Field
The invention relates to the technical field of polycarboxylic acid water reducing agents for cement concrete, in particular to an early-strength polycarboxylic acid water reducing agent prepared by an amidation reaction of an MOF structure and free radical polymerization and a method.
Background
Metal-organic frameworks (MOFs), as a very promising class of crystalline microporous materials, can be designed in their structure according to the targeted properties based on the geometry of the organic linker and the coordination mode of the inorganic metal ions or metal ion clusters. One key structural feature of MOFs is ultra-high porosity (up to 90% free volume) and incredibly high internal surface area, which plays a crucial role in functional applications. Typically, porous MOFs exhibit microporous characteristics (<2nm), however the pore size can be tuned in the range of a few angstroms to a few nanometers by controlling the length of the rigid organic linker. The research of the MOF composite material provides reference for synthesizing a high-performance composite material with a complex structure.
A MOF composite (hybrid) material is a material consisting of one MOF and one or more different component materials, including other MOFs, whose properties are significantly different from the materials of the individual components. In the composite material, the advantages of the MOFs (structural adaptability and flexibility, high porosity and ordered crystalline pores) and various functional materials (unique optical, electrical, magnetic and catalytic properties) can be effectively combined, so that new physical or chemical properties which cannot be obtained by a single component can be obtained, and the original properties can be enhanced. The selection of suitable MOF materials can be achieved using existing porous crystal libraries; or may use a simulation tool as an effective screening method.
To date, MOF composites, whose properties cannot be exhibited by individual components, have been successfully prepared using active materials including metal nanoparticles/nanorods (MNPs/MNRs), oxides, Quantum Dots (QDs), Polyoxometallates (POMs), polymers, graphene, Carbon Nanotubes (CNTs), and biomolecules, among others. Moreover, they offer the great advantage of flexible design, with the possibility of customizing the material to an optimal design. By perfect knowledge of the combined ingredients, porosity, functionality and morphology, it is meant that each MOF based composite is a new material with specific functional properties.
Disclosure of Invention
The invention aims to overcome the defects in the prior art and provide an early-strength polycarboxylic acid water reducer and a preparation method thereof, which improve the early-strength performance on the premise of high water reduction.
In order to realize the purpose, the invention adopts the following technical scheme:
the invention provides an early-strength polycarboxylic acid water reducing agent, which has the following structure:
wherein, P is N, NH or O atom; r1Is any one or combination of more of H, alkali metal ions, aliphatic groups, alicyclic groups or aromatic groups; r2，R3，R4，R6Respectively is any one or combination of more of H, aliphatic group, alicyclic group or aromatic group; r5Is any one or combination of several of aliphatic group, alicyclic group or aromatic group; the polymerization degrees r and q are respectively 9-200, and the polymerization degrees n, m and p are respectively 10-100.
In a preferable embodiment of the early strength type polycarboxylic acid water reducing agent of the present invention, the weight average molecular weight of the early strength type polycarboxylic acid water reducing agent is 20000 to 80000 g/mol.
The invention also provides a preparation method of the early-strength polycarboxylic acid water reducer, which comprises the following steps:
(1) preparing a water reducing agent prepolymerization product: carrying out water-phase oxidation-reduction free radical polymerization reaction on an unsaturated acid or derivative monomer thereof, an unsaturated polyether macromonomer or an unsaturated ester macromonomer at 5-45 ℃ under the combined action of an initiator, a reducing agent and a chain transfer agent for 3-5 hours to obtain a water reducing agent prepolymerization product; wherein the molar ratio of the unsaturated acid or derivative monomer thereof, the unsaturated polyether macromonomer or unsaturated ester macromonomer, the initiator, the reducing agent and the chain transfer agent is (3-5): 1: (0.03-0.1): (0.03-0.2): (0.03-0.1);
(2) preparing an early strength polycarboxylic acid water reducer: carrying out amidation reaction on the water reducing agent prepolymerization product prepared in the step (1) and metal-organic framework (MOF) nanocrystals containing amino, and adding water after 0.5-5 h to obtain an early strength polycarboxylic acid water reducing agent with the weight concentration of 10-60%; wherein the molar ratio of the water reducing agent prepolymerization product to the metal-organic framework (MOF) nanocrystal containing amino is 1: (1-10).
As a preferable embodiment of the preparation method of the present invention, the unsaturated acid or derivative monomer thereof in the step (1) is one or a combination of two or more of acrylic acid, methacrylic acid, aconitic acid, maleic acid, itaconic acid, dimethyl maleic acid, 2-dimethyl-succinic acid, allyl succinic acid, 2-buten-1-ylsuccinic acid, or 1,2,3, 4-cyclopentenetetracarboxylic acid.
As a preferable scheme of the preparation method, the unsaturated polyether macromonomer or unsaturated ester macromonomer in the step (1) is one or a combination of two or more of allyl polyethylene glycol, methallyl polyethylene glycol, isopentenol polyoxyethylene ether, isobutenol polyoxyethylene ether, methoxy polyethylene glycol methacrylate, methoxy polyethylene glycol acrylate, polyethylene glycol acrylate monoester and polyethylene glycol methacrylate, and the weight average molecular weight of the unsaturated polyether macromonomer or unsaturated ester macromonomer is 300-8000 g/mol.
As a preferable scheme of the preparation method, the initiator in the step (1) is one or a combination of more than two of hydrogen peroxide, ammonium persulfate, sodium persulfate and potassium persulfate.
In a preferable embodiment of the preparation method of the present invention, the reducing agent in step (1) is one or a combination of two or more of sodium bisulfite, sodium sulfite, sodium formaldehyde sulfoxylate, ascorbic acid, sodium ascorbate, isoascorbic acid, and sodium hypophosphite.
As a preferable scheme of the preparation method, the chain transfer agent in the step (1) is one or a combination of more than two of thioglycolic acid, 2-mercaptopropionic acid, 3-mercaptopropionic acid, sodium methallylsulfonate and dodecanethiol.
As a preferable scheme of the preparation method of the present invention, the structure of the metal-organic framework (MOF) nanocrystals containing amine groups in step (2) is simply represented by:
wherein M is a metal ion, preferably one or a combination of two of aluminum-organic framework (MOF) nanocrystals, magnesium-organic framework (MOF) nanocrystals.
According to the invention, the MOF is grafted to the molecular structure of the polycarboxylic acid type concrete high-performance water reducing agent, compared with the traditional water reducing agent, the process is simple, and a new function is endowed to the water reducing agent.
The invention has the following beneficial effects:
1. the raw materials used by the invention have rich sources.
2. The polycarboxylic acid water reducing agent prepared by the invention can release aluminum/magnesium ions through a metal-organic framework (MOF) in a molecular structure under the alkaline condition of concrete to shorten the setting time of the concrete, thereby improving the early strength of the concrete.
3. The polycarboxylic acid water reducing agent product prepared by the invention has early strength performance on the premise of not influencing water reduction.
4. The preparation method disclosed by the invention is safe and reliable in the whole process of preparing the polycarboxylate superplasticizer product, simple and convenient in operation steps, free of organic solvent, non-toxic, pollution-free and environment-friendly.
5. The invention can adjust the product performance by controlling the molecular structure of the water reducing agent copolymerization product and the grafting quantity of metal-organic framework (MOF) nanocrystals; the research of the polycarboxylic acids high efficiency water reducing agent with MOF structure is a breakthrough of the traditional water reducing agent technology, and the designability of the molecular structure layer enables the polycarboxylic acids high efficiency water reducing agent to be capable of developing series products with different performance characteristics or novel structures so as to meet the diversified requirements of building engineering on concrete admixtures, thereby having wider development potential and market prospect.
6. The polycarboxylic acid water reducing agent prepared by the invention is stable in performance after being prepared into an aqueous solution, and is not layered or precipitated during storage.
Detailed Description
In order to make the technical objects, technical solutions and advantages of the present invention more apparent, the present invention will be further described with reference to various embodiments.
Example 1
1) Preparing a water reducing agent prepolymerization product: under the combined action of 0.1mol of hydrogen peroxide, 0.05mol of sodium formaldehyde sulfoxylate and 0.03mol of 2-mercaptopropionic acid, 3mol of acrylic acid, 1mol of allyl polyethylene glycol (with the weight-average molecular weight of 300g/mol) are kept at the temperature of 5 ℃ for 5 hours, and a pre-polymerization product of the water reducing agent is obtained;
2) preparing an early strength polycarboxylic acid water reducer: carrying out amidation reaction on 1mol of the water reducing agent prepolymer obtained in the step 1) and 10mol of magnesium-organic framework (MOF) nanocrystals for 5 hours, and adding water to obtain the early-strength polycarboxylic acid water reducing agent with the concentration of 50 wt%, wherein the weight-average molecular weight is 20000 g/mol.
The molecular structural formula is as follows:
example 2
1) Preparing a water reducing agent prepolymerization product: carrying out redox free radical polymerization on 3mol of methacrylic acid and 1mol of methallyl polyethylene glycol (with the weight average molecular weight of 800g/mol) at 15 ℃ for 4 hours under the action of 0.08mol of ammonium persulfate, 0.1mol of sodium sulfite and 0.04mol of mercaptoethanol to obtain a pre-polymerization product of the water reducer;
2) preparing an early strength polycarboxylic acid water reducer: carrying out amidation reaction on 1mol of the water reducer prepolymer obtained in the step 1) and 7mol of magnesium-organic framework (MOF) nanocrystals for 3 hours, and adding water to obtain the early-strength polycarboxylic acid water reducer with the concentration of 50 wt%, wherein the weight-average molecular weight is 40000 g/mol.
The molecular structural formula is as follows:
example 3
1) Preparing a water reducing agent prepolymerization product: carrying out redox free radical polymerization on 4mol of sodium acrylate, 1mol of prenyl polyoxyethylene ether (with the weight-average molecular weight of 1000g/mol), 0.06mol of sodium persulfate, 0.15mol of sodium metabisulfite and 0.05mol of dodecanethiol for 3 hours at the temperature of 45 ℃ under the combined action of the sodium persulfate, the sodium metabisulfite and the dodecanethiol for 3 hours to obtain a pre-polymerization product of the water reducer;
2) carrying out amidation reaction on 1mol of the pre-polymerization product of the water reducing agent obtained in the step 1) and 6mol of magnesium-organic framework (MOF) nanocrystals for 4 hours, and adding water to obtain the early-strength polycarboxylic acid water reducing agent with the concentration of 50 wt%, wherein the weight-average molecular weight is 30000 g/mol.
The molecular structural formula is as follows:
example 4
1) Preparing a water reducing agent prepolymerization product: 5mol of sodium methacrylate, 1mol of isobutylene alcohol polyoxyethylene ether (weight average molecular weight is 1200g/mol), and under the combined action of 0.04mol of potassium persulfate, 0.1mol of sodium bisulfite and 0.1mol of sodium methyl propenyl sulfonate, the mixture is kept at the temperature of 35 ℃ for 3 hours to carry out redox free radical polymerization reaction, thus obtaining a prepolymerization product of the water reducing agent;
2) preparing an early strength polycarboxylic acid water reducer: carrying out amidation reaction on 1mol of the pre-polymerization product of the water reducing agent obtained in the step 1) and 5mol of magnesium-organic framework (MOF) nanocrystals for 4.5 hours, and adding water to obtain the early-strength polycarboxylic acid water reducing agent with the concentration of 60 wt%, wherein the weight-average molecular weight is 40000 g/mol.
The molecular structural formula is as follows:
example 5
1) Preparing a water reducing agent prepolymerization product: carrying out redox free radical polymerization on 3mol of acrylamide and 1mol of methoxypolyethylene glycol methacrylate (the weight average molecular weight is 3000g/mol) at 30 ℃ for 3 hours under the combined action of 0.05mol of hydrogen peroxide, 0.15mol of ferrous pyrophosphate and 0.08mol of 3-mercaptopropionic acid to obtain a water reducer prepolymer product;
2) preparing an early strength polycarboxylic acid water reducer: carrying out amidation reaction on 1mol of the pre-polymerization product of the water reducing agent obtained in the step 1) and 5mol of aluminum-organic framework (MOF) nanocrystals for 3.5 hours, and adding water to obtain the early-strength polycarboxylic acid water reducing agent with the concentration of 45 wt%, wherein the weight-average molecular weight is 60000 g/mol.
The molecular structural formula is as follows:
example 6
1) Preparing a water reducing agent prepolymerization product: carrying out redox free radical polymerization on 4mol of methacrylamide, 1mol of methoxypolyethylene glycol acrylate (with the weight-average molecular weight of 5000g/mol) at 10 ℃ for 5 hours under the combined action of 0.03mol of ammonium persulfate, 0.2mol of ferrous sulfate and 0.07mol of thioglycolic acid to obtain a water reducer prepolymerization product;
2) preparing an early strength polycarboxylic acid water reducer: carrying out amidation reaction on 1mol of the pre-polymerization product of the water reducing agent obtained in the step 1) and 4mol of aluminum-organic framework (MOF) nanocrystals for 3 hours, and adding water to obtain the early-strength polycarboxylic acid water reducing agent with the concentration of 40 wt%, wherein the weight-average molecular weight is 80000 g/mol.
The molecular structural formula is as follows:
example 7
1) Preparing a water reducing agent prepolymerization product: 5mol of potassium acrylate, 1mol of polyethylene glycol acrylate monoester (weight average molecular weight is 8000g/mol), and under the combined action of 0.06mol of sodium persulfate, 0.1mol of sodium hypophosphite and 0.03mol of mercaptoethanol, the mixture is kept at the temperature of 45 ℃ for 5 hours to carry out redox free radical polymerization reaction, thus obtaining a pre-polymerization product of the water reducing agent;
2) preparing an early strength polycarboxylic acid water reducer: carrying out amidation reaction on 1mol of the water reducing agent prepolymer obtained in the step 1) and 3mol of aluminum-organic framework (MOF) nanocrystals for 2 hours, and adding water to obtain the early-strength polycarboxylate water reducing agent with the concentration of 30 wt%, wherein the weight-average molecular weight is 45000 g/mol.
The molecular structural formula is as follows:
example 8
1) Preparing a water reducing agent prepolymerization product: carrying out redox free radical polymerization on 3.5mol of acrylic acid, 0.7mol of prenol polyoxyethylene ether (with the weight-average molecular weight of 3000g/mol) and 0.3mol of isobutenol polyoxyethylene ether (with the weight-average molecular weight of 2400g/mol) at 35 ℃ for 5 hours under the combined action of 0.05mol of sodium persulfate, 0.02mol of ascorbic acid and 0.03mol of mercaptoethanol to obtain a water reducer prepolymerization product;
2) preparing an early strength polycarboxylic acid water reducer: carrying out amidation reaction on 1mol of the water reducer prepolymer obtained in the step 1) and 2mol of aluminum-organic framework (MOF) nanocrystals for 3 hours, and adding water to obtain the early-strength polycarboxylic acid water reducer with the concentration of 50 wt%, wherein the weight-average molecular weight is 30000 g/mol.
The molecular structural formula is as follows:
example 9
1) Preparing a water reducing agent prepolymerization product: carrying out redox free radical polymerization on 5mol of 4-vinylbenzoic acid, 1mol of polyethylene glycol methacrylate (with the weight-average molecular weight of 6000g/mol), 0.07mol of potassium persulfate, 0.03mol of sodium ascorbate and 0.1mol of 2-mercaptopropionic acid for 5 hours at the temperature of 35 ℃ to obtain a water reducer pre-product;
2) preparing an early strength polycarboxylic acid water reducer: carrying out amidation reaction on 1mol of the water reducer pre-product obtained in the step 1) and 1mol of aluminum-organic framework (MOF) nanocrystals for 3 hours, and adding water to obtain the early-strength polycarboxylic acid water reducer with the concentration of 50 wt%, wherein the weight-average molecular weight is 35000 g/mol.
The molecular structural formula is as follows:
test example
1. Concrete set time test
The samples obtained in examples 1 to 9 were subjected to a setting time test with reference to GB8076-2008 "concrete admixture", and the results are shown in Table 1, assuming that a common polycarboxylic acid water reducing agent was used as a blank. It can be seen that the early-strength polycarboxylate water reducer prepared by grafting metal-organic framework (MOF) nanocrystals obviously shortens the initial and final setting time of concrete, and the higher the grafting content of the metal-organic framework (MOF) nanocrystals, the shorter the initial and final setting time. This is mainly because the structure of metal-organic framework (MOF) nanocrystals is broken down under alkaline conditions to release metal ions to promote cement hydration, resulting in a shortened setting time.
TABLE 1 clotting times of different samples
2. Neat paste fluidity test
The samples obtained in examples 1 to 9 were subjected to a net flow test with reference to GB8077-2000 "method for testing homogeneity of concrete admixtures", and the results are shown in Table 2. The W/C is 0.29, the broken and fixed mixing amount of the admixture is 0.11 percent of the cement using amount, the net slurry fluidity loss is increased within 0.5 hour, and the net slurry loss is accelerated within 0.5 hour mainly due to the shortened setting time.
TABLE 2 Net paste fluidity and loss over time for different samples
3. Testing of concrete Properties
The samples obtained in examples 1 to 9 were tested for slump loss and early strength of concrete with reference to GB8076-2008 "concrete admixture", and the results are shown in Table 3. When the folded and fixed mixing amount of the admixture is 1.5 wt% (relative to the cement dosage), the water reducing rate is higher than 40%, the compression strength is improved by more than 100% in 8h, more than 92% in 16h and more than 57% in 24h due to the shortened setting time.
TABLE 3 concrete slump retaining and early mechanical properties of different samples
It is to be understood that the above-described embodiments are only some of the presently preferred embodiments of the invention, and not all of them. Modifications, substitutions and improvements based on the embodiments of the present invention may be made by those skilled in the art without any creative effort, and all of them are within the protection scope of the present invention.
Claims (10)
1. An early strength type polycarboxylic acid water reducing agent, which has the following structure:
wherein, P is N, NH or O atom; r1Is any one or combination of more of H, alkali metal ions, aliphatic groups, alicyclic groups or aromatic groups; r2，R3，R4，R6Respectively is any one or combination of more of H, aliphatic group, alicyclic group or aromatic group; r5Is any one or combination of several of aliphatic group, alicyclic group or aromatic group; the polymerization degrees r and q are respectively 9-200, and the polymerization degrees n, m and p are respectively 10-100.
2. The early strength polycarboxylic acid water reducer according to claim 1, characterized in that the weight average molecular weight of the early strength polycarboxylic acid water reducer is 20000 to 80000 g/mol.
3. A preparation method of an early-strength polycarboxylic acid water reducer comprises the following steps:
(1) preparing a water reducing agent prepolymerization product: carrying out water-phase oxidation-reduction free radical polymerization reaction on an unsaturated acid or derivative monomer thereof, an unsaturated polyether macromonomer or an unsaturated ester macromonomer at 5-45 ℃ under the combined action of an initiator, a reducing agent and a chain transfer agent for 3-5 hours to obtain a water reducing agent prepolymerization product; wherein the molar ratio of the unsaturated acid or derivative monomer thereof, the unsaturated polyether macromonomer or unsaturated ester macromonomer, the initiator, the reducing agent and the chain transfer agent is 3-5: 1: 0.03-0.1: 0.03 to 0.2: 0.03 to 0.1;
(2) preparing an early strength polycarboxylic acid water reducer: carrying out amidation reaction on the water reducer prepolymer prepared in the step (1) and metal-organic framework MOF nanocrystals containing amino groups, and adding water after 0.5-5 h to obtain an early-strength polycarboxylate water reducer with the weight concentration of 10-60%; wherein the molar ratio of the water reducing agent prepolymerization product to the metal-organic framework MOF nanocrystal containing amino is 1: 1 to 10.
4. The method for preparing an early strength polycarboxylic acid water reducer according to claim 3, wherein the unsaturated acid or its derivative monomer in step (1) is one or a combination of two or more of acrylic acid, methacrylic acid, aconitic acid, maleic acid, itaconic acid, dimethyl maleic acid, 2-dimethyl-succinic acid, allyl succinic acid, 2-buten-1-ylsuccinic acid, and 1,2,3, 4-cyclopentenetetracarboxylic acid.
5. The preparation method of the early strength polycarboxylate water reducer according to claim 3, wherein the unsaturated polyether macromonomer or unsaturated ester macromonomer in step (1) is one or a combination of two or more of allyl polyethylene glycol, methallyl polyethylene glycol, prenol polyoxyethylene ether, isobutenol polyoxyethylene ether, methoxy polyethylene glycol methacrylate, methoxy polyethylene glycol acrylate, polyethylene glycol acrylate monoester and polyethylene glycol methacrylate, and the weight average molecular weight is 300-8000 g/mol.
6. The preparation method of the early strength polycarboxylate water reducer according to claim 3, wherein the initiator in step (1) is one or a combination of more than two of hydrogen peroxide, ammonium persulfate, sodium persulfate and potassium persulfate.
7. The method for preparing the early strength polycarboxylic acid water reducing agent according to claim 3, wherein the reducing agent in step (1) is one or a combination of two or more of sodium bisulfite, sodium sulfite, sodium formaldehyde sulfoxylate, ascorbic acid, sodium ascorbate, isoascorbic acid and sodium hypophosphite.
8. The method for preparing the early strength type polycarboxylic acid water reducing agent according to claim 3, wherein the chain transfer agent in step (1) is one or a combination of two or more of thioglycolic acid, 2-mercaptopropionic acid, 3-mercaptopropionic acid, sodium methallylsulfonate and dodecanethiol.
9. The method for preparing the early strength type polycarboxylic acid water reducing agent according to claim 3, wherein the metal-organic compound containing amino group in the step (2)The structural formula of the framework MOF nanocrystals is:
wherein M is a metal ion.
10. The preparation method of the early strength polycarboxylate water reducer according to claim 3 or 9, wherein the metal-organic framework MOF nanocrystals containing amine groups in step (2) are aluminum-organic framework MOF nanocrystals, magnesium-organic framework MOF nanocrystals or a combination of two of them.
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| CN114853383A (en) * | 2022-05-20 | 2022-08-05 | 唐山冀东水泥外加剂有限责任公司 | Polycarboxylate superplasticizer and preparation method thereof |
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| JP2007238387A (en) * | 2006-03-09 | 2007-09-20 | Nippon Shokubai Co Ltd | Powdery cement dispersant |
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