CN112876667A - Ferrocene modified polyoxyethylene ether monomer, ferrocene modified mud-resistant polycarboxylic acid water reducer and preparation method - Google Patents
Ferrocene modified polyoxyethylene ether monomer, ferrocene modified mud-resistant polycarboxylic acid water reducer and preparation method Download PDFInfo
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- CN112876667A CN112876667A CN202110145395.4A CN202110145395A CN112876667A CN 112876667 A CN112876667 A CN 112876667A CN 202110145395 A CN202110145395 A CN 202110145395A CN 112876667 A CN112876667 A CN 112876667A
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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
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
- C08G65/26—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds
- C08G65/2603—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds the other compounds containing oxygen
- C08G65/2606—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds the other compounds containing oxygen containing hydroxyl groups
- C08G65/2609—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds the other compounds containing oxygen containing hydroxyl groups containing aliphatic hydroxyl groups
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- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B24/00—Use of organic materials as active ingredients for mortars, concrete or artificial stone, e.g. plasticisers
- C04B24/40—Compounds containing silicon, titanium or zirconium or other organo-metallic compounds; Organo-clays; Organo-inorganic complexes
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
- C08F283/06—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polyethers, polyoxymethylenes or polyacetals
- C08F283/065—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polyethers, polyoxymethylenes or polyacetals on to unsaturated polyethers, polyoxymethylenes or polyacetals
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- 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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- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
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Abstract
The invention discloses a ferrocene modified polyoxyethylene ether monomer, a ferrocene modified mud-resistant polycarboxylic acid water reducer and a preparation method thereof, and the preparation method comprises the following steps: (1) under the combined action of enol and a catalyst, ferrocene epoxy monomer and ethylene oxide undergo ring-opening polymerization to prepare a ferrocene modified polyoxyethylene ether monomer; (2) under the combined action of an initiator, a reducing agent and a chain transfer agent, the ferrocene modified polyoxyethylene ether monomer, the unsaturated acid or the derivative monomer thereof are subjected to free radical random copolymerization to prepare the ferrocene modified polycarboxylic acid water reducing agent. The polycarboxylic acid water reducer prepared by the method is a mud-resistant polycarboxylic acid water reducer, and the surface adsorption and intercalation adsorption of clay on the polycarboxylic acid water reducer are inhibited by utilizing the steric hindrance effect of ferrocene groups on long side chains of a polymer, so that the anti-adsorption capacity of the water reducer on the clay is improved.
Description
Technical Field
The invention relates to the technical field of polycarboxylic acid water reducing agents for cement concrete, in particular to a mud-resistant polycarboxylic acid water reducing agent prepared from ferrocene modified polyoxyethylene ether monomers and a preparation method thereof.
Background
With the rapid development of domestic infrastructure, the demand of sand and stone materials is increased greatly, but due to the gradual control of the country on sand and stone exploitation and the protection of ecological environment, high-quality sand and stone aggregate resources are in more and more shortage, the price is also increased continuously, so that more and more projects are forced to use the sand and stone materials with poorer quality. Compared with water reducers such as naphthalene water reducers, melamine water reducers, sulfamates and the like, common polycarboxylic acid water reducers are more sensitive to the mud content of aggregates due to the comb-shaped structure, have poor material adaptability, often cause the phenomena of great reduction of the flowing property, acceleration of the loss of slump with time and the like of newly mixed concrete, and greatly reduce the performance and the using effect of the polycarboxylic acid water reducers. Therefore, aiming at the physicochemical properties of mud (mainly clay such as bentonite, montmorillonite, kaolin and the like), the mud-resistant polycarboxylic acid water reducer which is insensitive to mud contained in sandstone aggregate is developed, the adverse effect of mud on concrete is weakened or eliminated, and the mud-resistant polycarboxylic acid water reducer has great practical significance and economic value.
The patent CN110760037A discloses an amino acid modified mud-resistant polycarboxylate water reducer, which is characterized in that maleic anhydride, polyethylene glycol, epichlorohydrin and amino acid are sequentially subjected to esterification reaction, ring-opening reaction and substitution reaction under the solvent-free condition to prepare amino acid modified unsaturated acid ester, the amino acid modified unsaturated acid ester is polymerized with unsaturated carboxylic acid and isoamylol polyoxyethylene ether, and the adsorption and intercalation of the polycarboxylate water reducer in a long side chain terminal clay steric hindrance effect are reduced by utilizing the polycarboxylate water reducer. However, the process for synthesizing the amino acid modified unsaturated acid ester is very complicated, and the yield is limited by three-step reaction preparation.
Patent CN107325234B discloses an anti-mud type phosphate group modified polycarboxylate water reducing agent, utilizes diphenyl phosphoryl chloride to modify the polycarboxylate performed polymer that contains carboxyl for benzene ring is taken to some short side chain end, utilizes the intercalation of steric hindrance effect reduction polycarboxylate water reducing agent to adsorb, plays certain anti-mud effect. However, the diphenyl phosphoryl chloride used in the synthesis method is unstable and easy to hydrolyze, and the reaction conditions are harsh. In addition, the steric effect provided by the short side chain is limited, and the inhibition capability on the long side chain intercalation adsorption of the polycarboxylic acid water reducing agent is insufficient.
Disclosure of Invention
The invention aims to overcome the defects in the prior art and provide a ferrocene modified polyoxyethylene ether monomer and a method for preparing a mud-resistant polycarboxylic acid water reducer by using the same, which improve the mud resistance on the premise of reducing water.
The technical scheme is as follows: in order to achieve the purpose, the invention provides a ferrocene modified polyoxyethylene ether monomer, which has the following structure:
wherein R is1Represents H or CH3(ii) a x, y and z are integers, x is taken from 1-2, y is taken from 5-100, and z is taken from 1-10.
The ferrocene modified mud-resistant polycarboxylic acid water reducer prepared by the ferrocene modified polyoxyethylene ether monomer has the following structure:
wherein R is1、R2Represents H or CH3;R3Represents any one of H, alkali metal ions or alkyl with 1-5 carbon atoms and derivatives thereof; r4Represents H, COOM or CH2COOM, M represents H or alkali metal ion; m, n, x, y and z are integers, m, n and y are independently selected from 5-100, x is selected from 1-2, and z is selected from 1-10.
The invention provides a method for preparing a mud-resistant polycarboxylic acid water reducer, which comprises the following steps:
(1) preparing a ferrocene modified polyoxyethylene ether monomer: adding an initiator and a catalyst into a high-pressure reaction kettle, adding ethylene oxide and a ferrocene-containing epoxy monomer, and carrying out ring-opening polymerization reaction for 4-8 hours at 100-140 ℃ to obtain a ferrocene modified polyoxyethylene ether monomer; wherein the molar ratio of the ethylene oxide to the ferrocene-containing epoxy monomer to the initiator to the catalyst is (10-100): (1-10): 1: (0.02-0.1);
(2) preparing a ferrocene modified mud-resistant polycarboxylic acid water reducer: carrying out free radical polymerization reaction on the ferrocene modified polyoxyethylene ether monomer prepared in the step (1) and an unsaturated acid or derivative monomer thereof at the temperature of 10-45 ℃ for 3-5 hours under the combined action of an initiator, a reducing agent and a chain transfer agent, and adding alkali to adjust the pH value to 6-7 to obtain the ferrocene modified mud-resistant polycarboxylic acid water reducer; wherein the mole ratio of the ferrocene modified polyoxyethylene ether monomer, the unsaturated acid or derivative monomer thereof, the initiator, the reducing agent and the chain transfer agent is 1: (2-7): (0.02-0.2): (0.01-0.1): (0.02-0.1).
As a preferable embodiment of the production method of the present invention, the initiator in the step (1) is at least one of allyl alcohol, methallyl alcohol, or prenol alcohol.
As a preferable mode of the preparation method of the present invention, at least one of sodium, potassium or sodium hydride is used as the catalyst in the step (1).
As a preferable scheme of the preparation method of the invention, the unsaturated macromonomer containing ferrocene group in the step (1) is diThe cyclopentadienyl iron glycidyl ether has a structural formula as follows:
as a preferable embodiment of the preparation method of the present invention, the unsaturated acid or derivative monomer thereof in step (2) is at least one of acrylic acid, methacrylic acid, maleic anhydride, monomethyl maleate, monoethyl maleate, and itaconic acid.
As a preferable scheme of the preparation method of the present invention, the initiator in the step (2) is at least one 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 (2) is at least one of ascorbic acid, sodium ascorbate, sodium bisulfite, sodium sulfite, and sodium formaldehyde sulfoxylate.
As a preferable embodiment of the preparation method of the present invention, the chain transfer agent in step (2) is at least one of mercaptoethanol, mercaptopropionic acid, sodium methallyl sulfonate, and sodium propylene sulfonate.
As a preferable embodiment of the preparation method according to the present invention, in the step (2), the base is at least one of sodium hydroxide or potassium hydroxide.
The method adopts the epoxy monomer containing ferrocene groups and ethylene oxide to prepare the ferrocene modified polyoxyethylene ether monomer through ring-opening polymerization, and then synthesizes the ferrocene modified polycarboxylic acid water reducing agent through free radical polymerization, the preparation process is simple, the water reducing agent is endowed with new functions, and the anti-adsorption capacity of the water reducing agent to clay is improved.
The invention has the following beneficial effects:
1. the raw materials used by the method have rich sources.
2. The polycarboxylic acid water reducing agent prepared by the method has stable product performance, and does not delaminate or precipitate after being stored for a long time.
3. The method can adjust the molecular structure of the product by controlling the proportion of the ferrocene-containing epoxy monomer and the ethylene oxide, thereby obtaining excellent performance.
4. According to the polycarboxylate water reducer product prepared by the method, the steric hindrance of the ferrocene group on the long side chain of the water reducer is utilized to inhibit the surface adsorption and intercalation adsorption of clay on the polycarboxylate water reducer, so that the clay adsorption resistance of the water reducer is improved.
5. The preparation method disclosed by the invention is safe in preparation process, simple in operation steps, non-toxic, pollution-free and environment-friendly.
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 ferrocene modified polyoxyethylene ether monomer: adding 1mol of allyl alcohol and 0.02mol of sodium into a high-pressure reaction kettle, adding 20mol of ethylene oxide and 3mol of ferrocenyl glycidyl ether, and carrying out ring-opening polymerization reaction for 5 hours at 110 ℃ to obtain an unsaturated macromonomer containing ferrocenyl groups;
(2) preparing a ferrocene modified mud-resistant polycarboxylic acid water reducer: carrying out free radical polymerization reaction on 1mol of the unsaturated macromonomer containing ferrocene groups prepared in the step (1) and 3mol of acrylic acid at 10 ℃ for 3 hours under the combined action of 0.02mol of sodium persulfate, 0.01mol of ascorbic acid and 0.02mol of mercaptopropionic acid, and adding sodium hydroxide to adjust the pH value to be 6 so as to obtain the ferrocene modified mud-resistant polycarboxylic acid water reducing agent:
example 2
(1) Preparing a ferrocene modified polyoxyethylene ether monomer: adding 1mol of isoamylene alcohol and 0.04mol of potassium into a high-pressure reaction kettle, adding 50mol of ethylene oxide and 5mol of ferrocenyl glycidyl ether, and carrying out ring-opening polymerization reaction for 6 hours at 125 ℃ to obtain an unsaturated macromonomer containing ferrocenyl groups;
(2) preparing a ferrocene modified mud-resistant polycarboxylic acid water reducer: carrying out free radical polymerization reaction on 1mol of the unsaturated macromonomer containing ferrocene groups prepared in the step (1) and 4mol of maleic anhydride under the combined action of 0.1mol of potassium persulfate, 0.04mol of sodium ascorbate and 0.06mol of sodium methallylsulfonate at 40 ℃ for 4 hours, and adding sodium hydroxide to adjust the pH value to be 7 so as to obtain the ferrocene modified mud-resistant polycarboxylic acid water reducer:
example 3
(1) Preparing a ferrocene modified polyoxyethylene ether monomer: adding 1mol of isoamylene alcohol and 0.05mol of sodium into a high-pressure reaction kettle, adding 10mol of ethylene oxide and 1mol of ferrocenyl glycidyl ether, and carrying out ring-opening polymerization reaction for 4 hours at 100 ℃ to obtain an unsaturated macromonomer containing ferrocenyl groups;
(2) preparing a ferrocene modified mud-resistant polycarboxylic acid water reducer: carrying out free radical polymerization reaction on 1mol of the unsaturated macromonomer containing ferrocene groups prepared in the step (1) and 2mol of methacrylic acid at 25 ℃ for 3 hours under the combined action of 0.06mol of sodium persulfate, 0.02mol of sodium formaldehyde sulfoxylate and 0.03mol of mercaptoethanol, and adding potassium hydroxide to adjust the pH value to 6.5 to obtain the ferrocene modified mud-resistant polycarboxylic acid water reducer:
example 4
(1) Preparing a ferrocene modified polyoxyethylene ether monomer: adding 1mol of methallyl alcohol and 0.1mol of sodium into a high-pressure reaction kettle, adding 100mol of ethylene oxide and 10mol of ferrocenyl glycidyl ether, and carrying out ring-opening polymerization reaction for 8 hours at 140 ℃ to obtain an unsaturated macromonomer containing ferrocenyl groups;
(2) preparing a ferrocene modified mud-resistant polycarboxylic acid water reducer: carrying out free radical polymerization reaction on 1mol of the unsaturated macromonomer containing ferrocene groups prepared in the step (1) and 6mol of itaconic acid at 45 ℃ for 5 hours under the combined action of 0.2mol of ammonium persulfate, 0.1mol of sodium bisulfite and 0.1mol of sodium allylsulfonate, and adding potassium hydroxide to adjust the pH value to 6.5 to obtain the ferrocene modified mud-resistant polycarboxylic acid water reducer:
example 5
(1) Preparing a ferrocene modified polyoxyethylene ether monomer: adding 1mol of isoamylene alcohol and 0.05mol of sodium hydride into a high-pressure reaction kettle, adding 30mol of ethylene oxide and 3mol of ferrocenyl glycidyl ether, and carrying out ring-opening polymerization reaction for 5 hours at 120 ℃ to obtain an unsaturated macromonomer containing ferrocenyl groups;
(2) preparing a ferrocene modified mud-resistant polycarboxylic acid water reducer: carrying out free radical polymerization reaction on 1mol of the unsaturated macromonomer containing ferrocene groups prepared in the step (1) and 6mol of monoethyl maleate under the combined action of 0.1mol of hydrogen peroxide, 0.03mol of ascorbic acid and 0.05mol of mercaptopropionic acid at 35 ℃ for 5 hours, and adding sodium hydroxide to adjust the pH value to 7 to obtain the ferrocene modified mud-resistant polycarboxylic acid water reducer:
example 6
(1) Preparing a ferrocene modified polyoxyethylene ether monomer: adding 1mol of isoamylene alcohol and 0.03mol of sodium into a high-pressure reaction kettle, adding 40mol of ethylene oxide and 6mol of ferrocenyl glycidyl ether, and carrying out ring-opening polymerization reaction for 6 hours at 130 ℃ to obtain an unsaturated macromonomer containing ferrocenyl groups;
(2) preparing a ferrocene modified mud-resistant polycarboxylic acid water reducer: carrying out free radical polymerization reaction on 1mol of the unsaturated macromonomer containing ferrocene groups prepared in the step (1) and 5mol of monomethyl maleate under the combined action of 0.12mol of ammonium persulfate, 0.06mol of sodium sulfite and 0.08mol of sodium methallylsulfonate at 40 ℃ for 5 hours, and adding potassium hydroxide to adjust the pH value to be 6 so as to obtain the ferrocene modified mud-resistant polycarboxylic acid water reducer:
example 7
(1) Preparing a ferrocene modified polyoxyethylene ether monomer: adding 1mol of allyl alcohol and 0.06mol of potassium into a high-pressure reaction kettle, adding 30mol of ethylene oxide and 5mol of ferrocenyl glycidyl ether, and carrying out ring-opening polymerization reaction for 5 hours at 120 ℃ to obtain an unsaturated macromonomer containing ferrocenyl groups;
(2) preparing a ferrocene modified mud-resistant polycarboxylic acid water reducer: carrying out free radical polymerization reaction on 1mol of the unsaturated macromonomer containing ferrocene groups prepared in the step (1) and 4mol of methacrylic acid at 15 ℃ for 4 hours under the combined action of 0.1mol of sodium persulfate, 0.03mol of ascorbic acid and 0.04mol of mercaptoethanol, and adding sodium hydroxide to adjust the pH value to be 6 so as to obtain the ferrocene modified mud-resistant polycarboxylic acid water reducer:
example 8
(1) Preparing a ferrocene modified polyoxyethylene ether monomer: adding 1mol of methyl allyl alcohol and 0.08mol of sodium hydride into a high-pressure reaction kettle, adding 60mol of ethylene oxide and 8mol of ferrocenyl glycidyl ether, and carrying out ring-opening polymerization reaction for 7 hours at 135 ℃ to obtain an unsaturated macromonomer containing ferrocenyl groups;
(2) preparing a ferrocene modified mud-resistant polycarboxylic acid water reducer: carrying out free radical polymerization reaction on 1mol of the unsaturated macromonomer containing ferrocene groups prepared in the step (1) and 7mol of acrylic acid under the combined action of 0.08mol of potassium persulfate, 0.05mol of sodium ascorbate and 0.07mol of mercaptopropionic acid at 20 ℃ for 5 hours, and adding potassium hydroxide to adjust the pH value to be 7 so as to obtain the ferrocene modified mud-resistant polycarboxylic acid water reducer:
and (3) testing the net slurry fluidity: the samples obtained in examples 1 to 8 were tested for net flow by reference to GB8077-2012, test method for homogeneity of concrete admixtures. The water-cement ratio is 0.29, the mixing amount of the water reducing agent is the bending and fixing mixing amount of the cementing material, and the mixing amount of the montmorillonite is 3 percent of the cement consumption. As can be seen from the following table, compared with the common polycarboxylic acid water reducing agent, the additive amount change required by the examples 1 to 8 prepared by the method to achieve the initial fluidity with little difference when montmorillonite is doped and not doped is small, and the loss of the net slurry fluidity is small with time, which shows that the ferrocene modified polycarboxylic acid water reducing agent has obvious effect on clay adsorption resistance.
TABLE 1 Net pulp fluidity and loss over time for different samples
Testing the performance of the concrete: the samples obtained in examples 1 to 8 were subjected to concrete tests in accordance with GB50080-2016 Standard test methods for the Properties of general concrete mixtures. The test is carried out by adopting conch cement with the mixing ratio (kg/m)3): cement, sand, stone and water, wherein the weight ratio of water reducer is 360:796:1014:160, the mixing amount of water reducer is the bending and fixing mixing amount of the cementing material, and the mixing amount of montmorillonite is 3% of the using amount of the cement. As can be seen from the following table, the mud resistance of the examples 1 to 8 prepared by the method is obviously superior to that of the common polycarboxylic acid water reducing agent, and the slump loss resistance is better, so that the ferrocene modified polycarboxylic acid water reducing agent has better mud resistance.
TABLE 2 concrete test data for different samples
Claims (11)
2. A ferrocene modified mud-resistant polycarboxylic acid water reducer has the following structure:
wherein R is1、R2Represents H or CH3;R3Represents any one of H, alkali metal ions or alkyl with 1-5 carbon atoms and derivatives thereof; r4Represents H, COOM or CH2COOM, M represents H or alkali metal ion; m, n, x, y and z are integers, m, n and y are independently selected from 5-100, x is selected from 1-2, and z is selected from 1-10.
3. The method for preparing the ferrocene-modified anti-mud polycarboxylic acid water reducer as claimed in claim 2, which comprises the following steps:
(1) preparing a ferrocene modified polyoxyethylene ether monomer: adding an initiator and a catalyst into a high-pressure reaction kettle, adding ethylene oxide and a ferrocene-containing epoxy monomer, and carrying out ring-opening polymerization reaction for 4-8 hours at 100-140 ℃ to obtain a ferrocene-group-containing unsaturated macromonomer; wherein the molar ratio of the ethylene oxide to the ferrocene-containing epoxy monomer to the initiator to the catalyst is (10-100): (1-10): 1: (0.02-0.1);
(2) preparing a ferrocene modified mud-resistant polycarboxylic acid water reducer: carrying out free radical polymerization reaction on the ferrocene modified polyoxyethylene ether monomer prepared in the step (1) and an unsaturated acid or derivative monomer thereof at the temperature of 10-45 ℃ for 3-5 hours under the combined action of an initiator, a reducing agent and a chain transfer agent, and adding alkali to adjust the pH value to 6-7 to obtain the ferrocene modified mud-resistant polycarboxylic acid water reducer; wherein the mole ratio of the ferrocene modified polyoxyethylene ether monomer, the unsaturated acid or derivative monomer thereof, the initiator, the reducing agent and the chain transfer agent is 1: (2-7): (0.02-0.2): (0.01-0.1): (0.02-0.1).
4. The method of claim 3, wherein the initiator in step (1) is at least one of allyl alcohol, methyl allyl alcohol, or prenol.
5. The method of claim 3, wherein the catalyst used in step (1) is at least one of sodium, potassium or sodium hydride.
7. the method according to claim 3, wherein the unsaturated acid or derivative monomer in step (2) is at least one of acrylic acid, methacrylic acid, maleic anhydride, monomethyl maleate, monoethyl maleate, and itaconic acid.
8. The method according to claim 3, wherein the initiator in the step (2) is at least one of hydrogen peroxide, ammonium persulfate, sodium persulfate and potassium persulfate.
9. The method of claim 3, wherein the reducing agent in step (2) is at least one of ascorbic acid, sodium ascorbate, sodium bisulfite, sodium sulfite, and sodium formaldehyde sulfoxylate.
10. The method of claim 3, wherein the chain transfer agent in step (2) is at least one of mercaptoethanol, mercaptopropionic acid, sodium methallylsulfonate, and sodium propylene sulfonate.
11. The method according to claim 3, wherein the alkali in the step (2) is at least one of sodium hydroxide and potassium hydroxide.
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