CN110759663A - Preparation method and application of anti-mud polycarboxylate superplasticizer - Google Patents
Preparation method and application of anti-mud polycarboxylate superplasticizer Download PDFInfo
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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
- C04B40/00—Processes, in general, for influencing or modifying the properties of mortars, concrete or artificial stone compositions, e.g. their setting or hardening ability
- C04B40/0028—Aspects relating to the mixing step of the mortar preparation
- C04B40/0039—Premixtures of ingredients
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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
- C08F2/00—Processes of polymerisation
- C08F2/38—Polymerisation using regulators, e.g. chain terminating agents, e.g. telomerisation
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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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- 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
- C08F4/00—Polymerisation catalysts
- C08F4/40—Redox systems
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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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Abstract
The invention relates to a preparation method and application of a mud-resistant polycarboxylate superplasticizer, wherein the preparation method specifically comprises the following steps: s1: preparing a mud-resistant polycarboxylate superplasticizer mother solution: adding an unsaturated polyether macromonomer, an unsaturated small monomer and a vinyl silane coupling agent into a desalted water solution, and carrying out free radical copolymerization reaction under the action of an oxidation-reduction initiator and a chain transfer agent to prepare an anti-mud polycarboxylic acid water reducer mother liquor; s2: preparing a finished product: and (4) compounding the anti-mud polycarboxylate superplasticizer mother liquor prepared in the step (S1) with sodium gluconate and an amino silane coupling agent to obtain the anti-mud polycarboxylate superplasticizer. The preparation method and the application of the anti-mud polycarboxylic acid water reducer provided by the invention have the advantages of low mixing amount, long slump retaining time and strong mud resistance as a cement dispersant, and have the advantages of high utilization rate of raw materials and simple synthesis process.
Description
Technical Field
The invention relates to the technical field of concrete admixtures, in particular to a preparation method and application of a mud-resistant polycarboxylic acid water reducer.
Background
The polycarboxylate water reducing agent is a high-performance water reducing agent, and is a cement dispersing agent in the application of cement concrete. The method is widely applied to projects such as highways, bridges, dams, tunnels, high-rise buildings and the like. The polycarboxylic acid water reducing agent is used as a third-generation water reducing agent in the concrete industry, and before the polycarboxylic acid additive appears, the polycarboxylic acid water reducing agent comprises a lignosulfonate additive, a naphthalene sulfonate formaldehyde condensate, a melamine formaldehyde polycondensate, an acetone sulfonate formaldehyde condensate, an amino sulfonate formaldehyde condensate and the like. The new generation of polycarboxylic acid high-efficiency water reducing agent overcomes the defects of the traditional water reducing agent, has the outstanding advantages of low mixing amount, good slump keeping performance, low concrete shrinkage, strong adjustability on molecular structure, high potential of high performance, no formaldehyde in the production process, environmental protection and the like, and becomes the most important product in the current concrete admixture market. The polycarboxylate superplasticizer is a comb-shaped water-soluble polymer, and consists of a main chain rich in carboxylic acid groups and side chains of polyoxyalkylene groups.
The common concrete is artificial stone which is prepared by taking cement as a main cementing material, adding water, sand, stones and chemical additives and mineral admixtures if necessary, mixing the materials according to a proper proportion, uniformly stirring, densely molding, curing and hardening. Along with the more and more importance of the country to the environmental protection problem, the management and control to aggregate grit material for the concrete is stricter and stricter, this just leads to aggregate for the concrete to be more and more scarce, and the quality of grit material is more and more poor on the market. The sandstone aggregate has great influence on the quality of concrete, wherein the prominent aspect is that the mud content of the sandstone material is larger and larger, the mud content in the sandstone material is mainly clay, and the main components comprise montmorillonite, illite, kaolin and the like, wherein the montmorillonite has the strongest adsorption on concrete admixtures, particularly water reducing agents, so that the using effect of the water reducing agents in the concrete is hindered, the application effect of the water reducing agents is influenced, and the workability of the concrete is deteriorated. As the polycarboxylate superplasticizer which is the most widely applied water reducer at present, when the polycarboxylate superplasticizer is used as a concrete water reducer in a sand-rock material with large mud content, the mixing amount is increased, the slump loss is accelerated, the workability of concrete is influenced, the performance is greatly influenced, and the research on the mud-resistant polycarboxylate superplasticizer with excellent performance is urgently needed.
Chinese patent document CN201610028121 discloses a preparation method and application of an anti-mud polycarboxylic acid water reducer, wherein the preparation method is obtained by carrying out free radical copolymerization reaction on a specific unsaturated acid monomer, a specific unsaturated polyether macromonomer and a PVP macromonomer containing a poly (N-vinyl pyrrolidone) chain, and the molar weight of the unsaturated polyether macromonomer is 50-100% of that of the PVP macromonomer. The mud-resistant polycarboxylate superplasticizer has the advantages of low mixing amount, high water reducing rate and strong mud resistance, the raw material utilization rate is high, but PVP macromonomer needs to be synthesized firstly, the solvent recovery is troublesome, and the polycarboxylate superplasticizer can be generated only by two-step reaction, so that the process is complicated.
Chinese patent document CN201810249461 provides a normal-temperature early-strength polycarboxylate superplasticizer for prefabricated parts and a preparation method thereof. The polycarboxylate water reducer is adsorbed on the surfaces of cement particles in a single-point or multi-point anchoring mode through carboxyl, phosphate groups, isocyanate end groups and silane coupling agent hydrolyzed oligomers under the actions of ionic bonds, covalent bonds, hydrogen bonds, Van der Waals force and the like, the adsorption mode is more diversified, the early strength of a prefabricated part can be improved, the demolding time of the prefabricated part is shortened, the turnover efficiency of a grinding tool is accelerated, the cost is greatly saved, and the application effect in a sand-stone material with high mud content is poor.
Chinese patent document CN201611067604 provides a high mud resistance type polycarboxylate water reducing agent, which introduces triallyl phosphite and dimethylamino propyl acrylamide as small monomers to participate in synthesizing the polycarboxylate water reducing agent, and aiming at the condition that the mud content of a sand material is higher (the total mud content of sand is about 6% -10%), under the same test environment, the concrete water reducing rate equivalent to that of common polycarboxylate is still achieved while the mixing amount is reduced, and the concrete slump retaining effect is better, and the concrete strength grade can be improved by 1-2. The same effect is achieved when the water reducer is used in combination with other polycarboxylic acid water reducers. But the reaction temperature is required to be above 60 ℃, the reaction materials need to be heated, the reaction requirement condition is high, and the production equipment requirement is high.
Disclosure of Invention
In order to overcome the defects in the prior art, the invention provides a preparation method and application of a mud-resistant polycarboxylate superplasticizer, and solves the technical problems of poor mud resistance, short slump retaining time, low raw material utilization rate and complex synthesis process of the existing mud-resistant polycarboxylate superplasticizer.
The invention is realized by the following technical scheme:
the preparation method of the anti-mud polycarboxylate superplasticizer specifically comprises the following steps:
s1: preparing a mud-resistant polycarboxylate superplasticizer mother solution: adding an unsaturated polyether macromonomer, an unsaturated small monomer and a vinyl silane coupling agent into a desalted water solution, and carrying out free radical copolymerization reaction under the action of an oxidation-reduction initiator and a chain transfer agent to prepare an anti-mud polycarboxylic acid water reducer mother liquor;
s2: preparing a finished product: and (4) compounding the anti-mud polycarboxylate superplasticizer mother liquor prepared in the step (S1) with sodium gluconate and an amino silane coupling agent to obtain the anti-mud polycarboxylate superplasticizer.
Further, the specific operation of step S1 is:
s11: fully mixing unsaturated polyether macromonomer, oxidant in an oxidation-reduction initiator and water, and heating to the reaction temperature of 25-50 ℃ in a protective atmosphere;
s12: dropwise adding a material A dropwise solution consisting of unsaturated small monomers and water into the mixed solution obtained in the step S11 for 1-3 h; and simultaneously dropwise adding a B material dropwise adding solution consisting of a reducing agent, a chain transfer agent and water in an oxidation-reduction initiator for 1.5-3.5 h, dropwise adding the B material 0.5h later than the A material, neutralizing the B material with a 32% liquid sodium hydroxide solution after finishing dropwise adding, reacting for 1-2 h at a constant temperature, adjusting the water replenishing to a polymerization concentration of 30-60%, and discharging.
Protective atmosphere of N2Or an inert shielding gas. The polymerization concentration refers to the sum of the mass percent concentrations of all monomers in the reaction mixed solution.
Further, the unsaturated polyether macromonomer described in step S1 has the structural formula:
Further, the unsaturated small monomer in step S1 is one or more of acrylic acid, methacrylic acid, fumaric acid, aconitic acid, 2-acrylamide-2-methylpropanesulfonic acid, acrylamide, maleic anhydride, hydroxyethyl acrylate, and hydroxypropyl acrylate; the molar weight of the unsaturated small monomer is 3-5 times of that of the unsaturated polyether large monomer.
Further, the vinyl silane coupling agent described in step S1 is vinyl trimethoxysilane, vinyl triethoxysilane, vinyl tris (2-methoxyethoxy) silane or methyl vinyl dimethoxysilane; the molar weight of the vinyl silane coupling agent is 0.3-2 times of that of the unsaturated polyether macromonomer.
Further, the chain transfer agent in step S1 is thioglycolic acid, mercaptopropionic acid, sodium methallylsulfonate, tert-dodecyl mercaptan, isopropanol or mercaptoethanol; the mass of the chain transfer agent is 1 per thousand-2% of that of the unsaturated polyether macromonomer.
Further, in the step S1, the oxidant in the oxidation-reduction initiator is hydrogen peroxide, ammonium persulfate or potassium persulfate; the reducing agent in the oxidation-reduction initiator is vitamin C, sodium bisulfite, sodium formaldehyde sulfoxylate or ferrous sulfate; the mass of the oxidation-reduction initiator is 1 per thousand-1% of that of the unsaturated polyether.
Further, the silane coupling with amino group described in step S2The structural formula of the agent is:
wherein R1 is-H, -OH or-CH3R2 and R3 are-CH2-or-CH2CH2-; preferably, R1 is-CH3(ii) a R2 and R3 are-CH2-; n is an integer of 1 to 2.
Further, the desalted aqueous solution in step S1 is prepared for an industrial water purifier, and the conductivity is less than 15 us/cm.
Further, the free radical copolymerization reaction in the step 1 is a water-based free radical copolymerization reaction, and the temperature of the water-based free radical copolymerization reaction is 25-50 ℃.
An application of a mud-resistant polycarboxylate superplasticizer as a cement dispersant.
Compared with the prior art, the invention has the beneficial effects that:
the preparation method and the application of the anti-mud polycarboxylic acid water reducing agent provided by the invention have excellent mud resistance, are particularly suitable for areas with high mud content of aggregates, have the advantages of low mixing amount, high water reduction and high slump loss resistance, and are simple in preparation process, green and environment-friendly in production process and low in cost.
Detailed Description
The following examples are presented to illustrate certain embodiments of the invention in particular and should not be construed as limiting the scope of the invention. The present disclosure may be modified from materials, methods, and reaction conditions at the same time, and all such modifications are intended to be within the spirit and scope of the present invention.
Example 1:
into a flask equipped with a stirrer were charged 300g of the above-mentioned 1200 molecular weight monomer, 0.1g of ferrous sulfate, 1.8g of 30% hydrogen peroxide solution and 230g of desalted water, and N was introduced2To remove O in the solution2Then stirring and heating to 25 ℃, and dropwise adding a material A mixed solution consisting of 36g of acrylic acid, 58g of hydroxyethyl acrylate, 18.5g of vinyl trimethoxy silane and 100g of desalted water at the temperature for 1.5 h; consists of mercaptoethanol 1.65g, vitamin C0.5 g and desalted water 130gAnd (3) dropwise adding the mixed solution of the material B for 2 hours, keeping the temperature for 2 hours after dropwise adding is finished, finally neutralizing the pH of the reaction solution with 32% sodium hydroxide solution to 6-8, and adjusting the pH to be the anti-mud polycarboxylate superplasticizer mother liquor KL-1 with the solid content of 40% by using desalted water.
250g of the anti-mud polycarboxylate superplasticizer mother liquor prepared by the method and a silane coupling agent with amino groups (R1 is-CH)3(ii) a R2 and R3 are-CH2-; n is 1)20 g and 10 g of sodium gluconate, 1000g of water is supplemented to adjust the solid content to 13 percent, and the material is discharged.
Example 2:
into a flask equipped with a stirrer were charged 300g of the above-mentioned 1200 molecular weight monomer, 0.1g of ferrous sulfate, 2.0g of 30% hydrogen peroxide solution and 230g of desalted water, and N was introduced2To remove O in the solution2Then stirring and heating to 25 ℃, and dropwise adding a material A mixed solution consisting of 54g of acrylic acid, 43.5g of hydroxyethyl acrylate, 23.75g of vinyl triethoxysilane and 100g of desalted water at the temperature for 1.5 h; and (3) adding a B material mixed solution consisting of 1.98g of mercaptopropionic acid, 0.6g of vitamin C pharmaceutical grade and 130g of desalted water for 2 hours, keeping the temperature for 2 hours after the addition is finished, neutralizing the pH of the reaction solution by using 32% sodium hydroxide solution to be 6-8, and adjusting the pH to be the anti-mud polycarboxylic acid water reducer KL-2 with the solid content of 40% by using desalted water.
250g of the anti-mud polycarboxylate superplasticizer mother liquor prepared by the method is taken, and the amino silane coupling agent (R1 is-CH)3(ii) a R2 and R3 are-CH2-; n is 1)20 g and 10 g of sodium gluconate, 1000g of water is supplemented to adjust the solid content to 13 percent, and the material is discharged.
Example 3:
into a flask equipped with a stirrer were charged 300g of the above-mentioned 1200 molecular weight monomer, 0.1g of ferrous sulfate, 2.0g of 30% hydrogen peroxide solution and 230g of desalted water, and N was introduced2To remove O in the solution2Then stirring and heating to 25 ℃, and dropwise adding a material A mixed solution consisting of 54g of acrylic acid, 43.5g of hydroxyethyl acrylate, 16.53g of methyl vinyl dimethoxy silane and 100g of desalted water at the temperature for 2 hours; a B material mixed solution consisting of 3.20g of sodium methallyl sulfonate, 0.6g of vitamin C pharmaceutical grade and 130g of desalted waterAnd (3) dropwise adding the solution for 2.5h, preserving heat for 2h after dropwise adding, finally neutralizing the reaction solution with 32% sodium hydroxide solution to obtain pH of 6-8, and adjusting the pH to obtain an anti-mud polycarboxylate superplasticizer mother solution KL-3 with solid content of 40% by using desalted water.
250g of the prepared mud-resistant polycarboxylate superplasticizer is taken, and the obtained polycarboxylate superplasticizer contains amino silane coupling agent (R1 is-CH)3(ii) a R2 and R3 are-CH2-; n-2) 20g and 10 g of sodium gluconate, and 1000g of water is supplemented until the solid content is adjusted to 13 percent, and then the material is discharged.
Comparative example 1:
comparative example 1 is a finished product of a commercially available anti-mud water reducing agent, and the solid content is 13%. When the cement mortar is applied and implemented, the adopted cement is conch cement PO42.5, the sand is medium sand with fineness modulus M of 2.6, and the stones are continuous graded broken stones with the grain size of 5-10 mm and 10-20 mm.
The polycarboxylic acid water reducing agents of examples 1-3 and comparative example 1 are used for measuring the fluidity of the net slurry according to GB/T8077-2012 'test method for homogeneity of concrete admixture', montmorillonites with different masses are used for replacing cement with corresponding masses according to an external mixing method, the commercial OCMA sodium-based bentonite is adopted, the water-cement ratio is fixed to be 0.29, the mixing amount of the water reducing agent is adjusted to ensure that the initial fluidity of the net slurry is between 200 and 250mm, and the results are shown in Table 1.
TABLE 1 Cement paste fluidity test results
As is clear from the results in Table 1, in the cement having a mud content of 0, the fluidity at the beginning of the slurry and after 30min was slightly superior to that of the comparative example when the admixture of the example was made comparable to that of the comparative example. With the increase of the mud content, the flow property of the net slurry can be kept basically unchanged only by increasing a small amount in the embodiment, while the initial flow degree of the comparative example is only about 200mm after the amount is greatly increased, the loss is extremely fast, and the flow degree is close to the loss after 60min, which shows that the polycarboxylic acid water reducer has excellent mud resistance.
The influence of the polycarboxylate superplasticizer of the embodiments 1-3 and the comparative example 1 on fresh concrete is determined by referring to relevant regulations of GB/T8076-2008 concrete admixture, the water-cement ratio is fixed to be 0.45, the mixing amount of the polycarboxylate superplasticizer is adjusted, the initial slump of the concrete is 210mm +/-10 mm, and the concrete weight mixing ratio is as follows: cement 260, mineral powder 50, fly ash 50, sand 760, large stone 650, small stone 430 and water 170. The results are shown in Table 2.
TABLE 2 concrete Performance test results
The results in Table 2 show that the concrete performance of examples 1-3 can still reach the level equivalent to or slightly higher than that of the comparative example under the condition that the mixing amount is far lower than that of the comparative example, for example, the initial slump of example 1/the comparative example is 230mm/220cm, the spreading degree is 580mm/570cm, the slump after 60min is 220mm/210mm, the spreading degree is 560mm/450mm, and the strength is slightly higher than that of the comparative example, which shows that the polycarboxylic acid water reducer of the invention has the advantages of high water reduction and high slump retention, and has no adverse effect on the strength.
In conclusion, the mud-resistant polycarboxylate superplasticizer of the application introduces the vinyl silane coupling agent on the basis of reasonably designing the water reducing group and the slow-release group in the synthesis process, synthesizes the mud-resistant polycarboxylate superplasticizer mother liquor, and introduces the silane coupling agent structure with amino group in the compounding process to obtain the finished mud-resistant polycarboxylate superplasticizer. Through free radical polymerization, silane groups are introduced to the main chain, the silane groups are hydrolyzed under the alkaline condition of concrete to form a silanol structure, a hydrophobic layer can be effectively formed on the clay surface, the adsorption of clay particles on the molecular structure of polycarboxylic acid is inhibited, and the water reducing effect of the polycarboxylic acid is obviously enhanced compared with the mud resistance of a common polycarboxylic acid water reducing agent. The silane coupling agent with amino groups is introduced by compounding, more than two strong adsorption amino groups are reserved in the silane coupling agent with amino groups, the silane coupling agent with amino groups is adsorbed on the surface of clay particles through charges to form firm chemical adsorption, and a double electric layer of compression and diffusion is used for preventing the clay from hydration and expansion; meanwhile, the amino-bearing silane coupling agent increases silicon hydroxyl groups, a hydrophobic layer can be effectively formed on the clay surface, a reasonable hydration film is effectively guaranteed on the clay surface, the hydration effect of the clay surface is prevented and slowed down, the amino-bearing silane coupling agent has strong inhibition and silanol film forming characteristics from the molecular structure, and the influence of clay particles on the workability of concrete is obviously reduced. Through the synergistic effect of two modes of synthesis and compounding, the water reducer disclosed by the invention has excellent mud resistance, the workability of concrete is well maintained, and the comprehensive effect is excellent.
The above description is only an 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 the present specification, or directly or indirectly applied to other related technical fields, are included in the scope of the present invention.
Claims (10)
1. The preparation method of the anti-mud polycarboxylate superplasticizer is characterized by comprising the following steps:
s1: preparing a mud-resistant polycarboxylate superplasticizer mother solution: adding an unsaturated polyether macromonomer, an unsaturated small monomer and a vinyl silane coupling agent into a desalted water solution, and carrying out free radical copolymerization reaction under the action of an oxidation-reduction initiator and a chain transfer agent to prepare an anti-mud polycarboxylic acid water reducer mother liquor;
s2: preparing a finished product: and (4) compounding the anti-mud polycarboxylate superplasticizer mother liquor prepared in the step (S1) with sodium gluconate and an amino silane coupling agent to obtain the anti-mud polycarboxylate superplasticizer.
2. The preparation method of the anti-mud type polycarboxylate superplasticizer according to claim 1, wherein the concrete operation of step S1 is:
s11: fully mixing unsaturated polyether macromonomer, oxidant in an oxidation-reduction initiator and water, and heating to the reaction temperature of 25-50 ℃ in a protective atmosphere;
s12: dropwise adding a material A dropwise solution consisting of unsaturated small monomers and water into the mixed solution obtained in the step S11 for 1-3 h; and simultaneously dropwise adding a B material dropwise adding solution consisting of a reducing agent, a chain transfer agent and water in an oxidation-reduction initiator for 1.5-3.5 h, dropwise adding the B material 0.5h later than the A material, neutralizing the B material with a 32% liquid sodium hydroxide solution after finishing dropwise adding, reacting for 1-2 h at a constant temperature, adjusting the water replenishing to a polymerization concentration of 30-60%, and discharging.
3. The preparation method of the anti-mud polycarboxylic acid water reducer according to claim 1, wherein the unsaturated polyether macromonomer in step S1 has a structural formula:
wherein R3 is-H, -OH or-CH3R4 is-CH2-or-CH2CH2And n is an integer of 25 to 65.
4. The preparation method of the anti-mud polycarboxylic acid water reducer according to claim 1, characterized in that the unsaturated small monomer in step S1 is one or more of acrylic acid, methacrylic acid, fumaric acid, aconitic acid, 2-acrylamide-2-methylpropanesulfonic acid, acrylamide, maleic anhydride, hydroxyethyl acrylate, and hydroxypropyl acrylate; the molar weight of the unsaturated small monomer is 3-5 times of that of the unsaturated polyether large monomer.
5. The method for preparing the anti-mud type polycarboxylate water reducer according to the claim 1, characterized in that the vinyl silane coupling agent in the step S1 is vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (2-methoxyethoxy) silane or methylvinyldimethoxysilane; the molar weight of the vinyl silane coupling agent is 0.3-2 times of that of the unsaturated polyether macromonomer.
6. The method for preparing the anti-mud type polycarboxylate superplasticizer according to claim 1, wherein the chain transfer agent in step S1 is thioglycolic acid, mercaptopropionic acid, sodium methallylsulfonate, tert-dodecyl mercaptan, isopropanol or mercaptoethanol; the mass of the chain transfer agent is 1 per thousand-2% of that of the unsaturated polyether macromonomer.
7. The preparation method of the anti-mud polycarboxylic acid water reducing agent according to claim 1, characterized in that the oxidant in the oxidation-reduction initiator in step S1 is hydrogen peroxide, ammonium persulfate or potassium persulfate; the reducing agent in the oxidation-reduction initiator is vitamin C, sodium bisulfite, sodium formaldehyde sulfoxylate or ferrous sulfate; the mass of the oxidation-reduction initiator is 1 per thousand-1% of that of the unsaturated polyether.
8. The method for preparing the anti-mud type polycarboxylate superplasticizer according to claim 1, wherein the structural formula of the silane coupling agent with amino group in step S2 is as follows:wherein R1 is-H, -OH or-CH3R2 and R3 are-CH2-or-CH2CH2-。
9. The preparation method of the anti-mud polycarboxylic acid water reducing agent according to claim 1, characterized in that the radical copolymerization in step 1 is an aqueous radical copolymerization, and the temperature of the aqueous radical copolymerization is 25-50 ℃.
10. The application of the anti-mud polycarboxylate superplasticizer prepared by the preparation method of any one of claims 1 to 9 as a cement dispersant.
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| CN111333367A (en) * | 2020-05-18 | 2020-06-26 | 湖南凝英新材料科技有限公司 | Preparation method of polycarboxylate superplasticizer |
| CN112062910A (en) * | 2020-09-09 | 2020-12-11 | 安徽海螺新材料科技有限公司 | Micro-crosslinking anti-mud polycarboxylate superplasticizer and preparation method thereof |
| CN113461360A (en) * | 2021-07-27 | 2021-10-01 | 湖南化工职业技术学院（湖南工业高级技工学校） | Preparation method of anti-mud polycarboxylate superplasticizer |
| CN113583174A (en) * | 2021-07-23 | 2021-11-02 | 安徽海螺新材料科技有限公司 | Preparation method of rheological agent special for concrete fine aggregate |
| CN113637122A (en) * | 2021-07-13 | 2021-11-12 | 湖南中岩建材科技有限公司 | Polycarboxylic acid compound and preparation method and application thereof |
| CN113754840A (en) * | 2021-10-12 | 2021-12-07 | 眉山海螺新材料科技有限公司 | Micro-crosslinking viscosity-reducing anti-mud polycarboxylate superplasticizer and preparation method thereof |
| CN114276499A (en) * | 2021-04-17 | 2022-04-05 | 厦门欣润岩新材料有限公司 | High-water-reducing slump-retaining polycarboxylate superplasticizer and preparation method thereof |
| 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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