Mud-resistant polycarboxylate superplasticizer and preparation method thereof

By introducing phosphate groups, quaternary ammonium salt groups, and sulfonic acid groups into polycarboxylate superplasticizers, their adsorption and tolerance properties on clay surfaces are improved. This solves the problem of reduced dispersion performance of polycarboxylate superplasticizers under the influence of soil, achieving better dispersibility and clay tolerance, and improving the early strength performance of concrete.

CN121064413APending Publication Date: 2025-12-05ZHEJIANG SANJIANG CHEM NEW MATERIALS CO LTD
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Patent Information

Application Number
CN202511293898.0
Authority / Receiving Office
CN · China
Patent Type
Applications(China)
Current Assignee / Owner
Filing Date
2025-09-11
Publication Date
2025-12-05

AI Technical Summary

Technical Problem

Existing polycarboxylate superplasticizers are affected by soil in concrete, resulting in reduced dispersion performance and poor performance, especially when the mud content of sand and gravel increases.

Method used

Introducing phosphate groups, quaternary ammonium salt groups, and sulfonic acid groups into the structure of polycarboxylate superplasticizer improves its adsorption and tolerance properties on clay surfaces. By combining ethylene glycol monoethylene ether polyoxyethylene ether macromonomers, small monomers containing carboxyl and vinyl groups, functional monomers containing phosphate and vinyl groups, and functional monomers containing quaternary ammonium, sulfonic acid, and vinyl groups, dispersibility and clay tolerance are optimized.

Benefits of technology

It improves the dispersibility and clay resistance of polycarboxylate superplasticizer, enhances the early strength of concrete, simplifies the production process, and facilitates industrial-scale mass production.

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Abstract

The invention relates to the technical field of synthesis of concrete water reducing agents, in particular to a mud-resistant polycarboxylic acid water reducing agent and a preparation method thereof. The mud-resistant polycarboxylic acid water reducer is prepared from an ethylene glycol monovinyl ether polyoxyethylene ether macromonomer A, a micromonomer B containing carboxyl and vinyl at the same time, a functional monomer C1 containing phosphate and vinyl at the same time, and a functional monomer C2 containing quaternary ammonium, sulfonic acid and vinyl at the same time, the small monomer B containing both carboxyl and vinyl comprises any one of acrylic acid, methacrylic acid, hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxyethyl methylacrylate and hydroxypropyl methacrylate; the functional monomer C1 containing the phosphate group and the vinyl group at the same time is 2-(methacryloyloxy) ethyl phosphate and / or 10-(2-methacryloyloxy) monodecyl phosphate. According to the invention, a phosphate group, a quaternary ammonium salt group and a sulfonic acid group are introduced into the structure of the polycarboxylate superplasticizer, so that the polycarboxylate superplasticizer is more easily adsorbed on the surface of clay and is not embedded into the layered structure of the clay, the dispersibility and adsorbability of the polycarboxylate superplasticizer and the tolerance of the clay are improved, and the early strength performance of concrete is improved.
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Description

TECHNICAL FIELD

[0001] The application relates to the technical field of concrete water-reducing agent synthesis, in particular to a mud-resistant polycarboxylate water-reducing agent and a preparation method thereof. BACKGROUND

[0002] In the application process of the polycarboxylate water-reducing agent, the polycarboxylate water-reducing agent is greatly affected by the mud in the concrete, which can reduce the dispersion performance of the polycarboxylate water-reducing agent on cement and greatly reduce the use effect of the polycarboxylate water-reducing agent. At present, the shortage of high-quality sand and gravel resources in China is serious, and the mud content of sand and gravel is generally increased. Therefore, improving the mud resistance of the polycarboxylate water-reducing agent has become an urgent practical problem in the industry. SUMMARY

[0003] In order to solve the technical problem that the dispersion performance of the polycarboxylate water-reducing agent on cement is reduced and the use effect of the polycarboxylate water-reducing agent is greatly reduced, the application provides a mud-resistant polycarboxylate water-reducing agent and a preparation method thereof.

[0004] The mud-resistant polycarboxylate water-reducing agent provided by the application is realized by the following technical scheme.

[0005] The mud-resistant polycarboxylate water-reducing agent comprises glycol monovinyl ether polyoxyethylene ether macromonomer A, small monomer B containing carboxyl and vinyl groups, functional monomer C1 containing phosphoric acid groups and vinyl groups, and functional monomer C2 containing quaternary ammonium groups, sulfonic acid groups and vinyl groups; the small monomer B containing carboxyl and vinyl groups comprises any one of acrylic acid, methacrylic acid, hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxyethyl methacrylate and hydroxypropyl methacrylate; the functional monomer C1 containing phosphoric acid groups and vinyl groups is 2-(methacryloyloxy)ethyl phosphate and / or 10-(2-methacryloyloxy) phosphonic acid monodecyl ester.

[0006] The application introduces phosphoric acid groups, quaternary ammonium salt groups and sulfonic acid groups into the structure of the polycarboxylate water-reducing agent, so that the polycarboxylate water-reducing agent is more easily adsorbed on the surface of clay and is not embedded in the layered structure of clay, the dispersion, adsorption and clay resistance of the polycarboxylate water-reducing agent are improved, and the early strength performance of the concrete is improved.

[0007] Preferably, the functional monomer C2 containing quaternary ammonium groups, sulfonic acid groups and vinyl groups has the following structural formula:

[0008] R1 in the C2 structural formula is -H or -CH3; R2 in the C2 structural formula is -CH2-, -CH2CH2-, -CH2CH2CH2- or -CH2CH2CH2CH2- 、-CH2CH2CH2CH2CH2-; R3 in the C2 formula is -CH2-, -CH2CH2-, -CH2CH2CH2-, -CH2CH2CH2CH2- 、 -CH2CH2CH2CH2CH2-.

[0009] By adopting the technical scheme, the quaternary ammonium salt and sulfonic acid group are introduced into the anti-mud polycarboxylate superplasticizer, so that the dispersibility, adsorbability and clay tolerance of the polycarboxylate superplasticizer are improved.

[0010] Further preferably, R2 in the C2 formula is -CH2CH2CH3; R3 in the C2 formula is -CH2CH2CH2- or -CH2CH2CH2CH2-.

[0011] Further preferably, the functional monomer C2 containing quaternary ammonium group, sulfonic acid group and vinyl group simultaneously is 3-[(3-acrylamidopropyl)dimethylammonio]propane-1-sulfonate and / or 4-[(3-methylacrylamidopropyl)dimethylammonio]butane-1-sulfonate.

[0012] Preferably, the molar ratio of the ethylene glycol monovinyl ether polyoxyethylene ether macromonomer A to the small monomer B containing carboxyl and vinyl groups simultaneously is 1:(3.5-4.25).

[0013] Preferably, the molar ratio of the ethylene glycol monovinyl ether polyoxyethylene ether macromonomer A to the functional monomer C1 containing phosphoric acid group and vinyl group simultaneously, the functional monomer C2 containing quaternary ammonium group, sulfonic acid group and vinyl group simultaneously is 1:(0.05-0.15):(0.10-0.20).

[0014] Further preferably, the molar ratio of the ethylene glycol monovinyl ether polyoxyethylene ether macromonomer A to the small monomer B containing carboxyl and vinyl groups simultaneously, the functional monomer C1 containing phosphoric acid group and vinyl group simultaneously, the functional monomer C2 containing quaternary ammonium group, sulfonic acid group and vinyl group simultaneously is 1:4:0.10:0.15.

[0015] Preferably, the weight average molecular weight Mw of the ethylene glycol monovinyl ether polyoxyethylene ether macromonomer A is 3000-6000.

[0016] Further preferably, the functional monomer C2 containing quaternary ammonium group, sulfonic acid group and vinyl group simultaneously is 3-[(3-acrylamidopropyl)dimethylammonio]propane-1-sulfonate and / or 4-[(3-methylacrylamidopropyl)dimethylammonio]butane-1-sulfonate; the functional monomer C1 containing phosphoric acid group and vinyl group simultaneously is 10-(2-methacryloyloxy)phosphonic acid monodecyl ester; and the small monomer B containing carboxyl and vinyl groups simultaneously is acrylic acid and / or methacrylic acid.

[0017] By adopting the technical scheme, the polycarboxylic acid water reducing agent is endowed with excellent dispersing performance, adsorbing performance and clay resistance.

[0018] The application provides a preparation method of the anti-mud polycarboxylic acid water reducing agent.

[0019] The preparation method of the anti-mud polycarboxylic acid water reducing agent comprises the following steps.

[0020] Step one, 10 parts of ethylene glycol monovinyl ether polyoxyethylene ether macromonomer A is fully dissolved in 10-20 parts of deionized water to obtain a macromonomer A aqueous solution;

[0021] Meanwhile, an initiator aqueous solution is prepared: 1-2 parts of ascorbic acid is fully dissolved in 18-19 parts of deionized water to obtain the initiator aqueous solution;

[0022] Meanwhile, a small monomer B aqueous solution is prepared: 10 parts of small monomer B containing a carboxyl group and a vinyl group, 0.25-2 parts of hydrogen peroxide and 0.5-2 parts of mercaptoethanol are fully dissolved in 20 parts of deionized water to obtain the small monomer B aqueous solution;

[0023] Meanwhile, a functional monomer C1 aqueous solution is prepared: 10 parts of functional monomer C1 containing a phosphoric acid group and a vinyl group, 0.25-2 parts of hydrogen peroxide, 0.25-1 part of ammonium persulfate and 0.5-2 parts of mercaptoethanol are fully dissolved in 20 parts of deionized water to obtain the functional monomer C1 aqueous solution;

[0024] Meanwhile, a functional monomer C2 aqueous solution is prepared: 10 parts of functional monomer C2 containing a quaternary ammonium group, a sulfonic acid group and a vinyl group, 0.25-1 part of hydrogen peroxide, 0.25-1 part of ammonium persulfate and 0.5-2 parts of mercaptoethanol are fully dissolved in 20 parts of deionized water to obtain the functional monomer C2 aqueous solution;

[0025] Step two, the temperature of the macromonomer A aqueous solution is controlled to be 20-40 DEG C through water bath heating, the initiator aqueous solution, the small monomer B aqueous solution, the functional monomer C1 aqueous solution and the functional monomer C2 aqueous solution are simultaneously added dropwise into the monomer A aqueous solution at a rotating speed of 100-250 rpm, and after the dropwise addition is completed, the reaction is maintained for 15-30 min at 20-40 DEG C, then 0.1-0.5 mol / L sodium hydroxide aqueous solution is added after the solution is cooled to room temperature, the pH value of the system is adjusted to be 6-8, and the anti-mud polycarboxylic acid water reducing agent can be obtained.

[0026] In the application, the high-activity ethylene glycol monovinyl ether polyoxyethylene ether macromonomer can be used to rapidly prepare the anti-mud polycarboxylic acid water reducing agent at 20-40 DEG C, the reaction can be carried out at normal temperature, the synthesis process is simple, and the industrialized batch production can be easily realized.

[0027] Preferably, the molar ratio of the ethylene glycol monovinyl ether polyoxyethylene ether macromonomer A in the aqueous solution of the macromonomer A in step two to the small monomer B containing carboxyl and vinyl in the aqueous solution of the small monomer B, the functional monomer C1 containing phosphoric acid group and vinyl in the aqueous solution of the functional monomer C1, the functional monomer C2 containing quaternary ammonium group, sulfonic acid group and vinyl in the aqueous solution of the functional monomer C2 is 1:(3.5-4.25):(0.05-0.15):(0.10-0.20), and the dropping completion time of the aqueous solution of the initiator, the aqueous solution of the small monomer B, the aqueous solution of the functional monomer C1, and the aqueous solution of the functional monomer C2 is uniformly 30-60 minutes.

[0028] By adopting the technical scheme, the small monomer B containing carboxyl and vinyl can be effectively consumed, the monomer conversion rate of the prepared polycarboxylic acid water reducing agent is ensured, the product yield of the polycarboxylic acid water reducing agent is improved, and the overall production cost is reduced.

[0029] In summary, the present application has the following advantages:

[0030] 1. By introducing phosphoric acid groups, quaternary ammonium salt groups and sulfonic acid groups into the structure of the polycarboxylic acid water reducing agent, the polycarboxylic acid water reducing agent is more easily adsorbed on the surface of clay and is not embedded in the layered structure of clay, thereby improving the dispersibility, adsorbability and clay resistance of the polycarboxylic acid water reducing agent, and facilitating the improvement of the early strength performance of concrete.

[0031] 2. The present application can be reacted at room temperature, and the synthesis process is simple, facilitating the realization of industrial mass production. DETAILED DESCRIPTION

[0032] In order to further understand the creativity and technical progress of the present application, the preferred embodiments of the present application are discussed in detail below in combination with examples and comparative examples.

[0033] Example: A clay-resistant polycarboxylic acid water reducing agent is prepared from ethylene glycol monovinyl ether polyoxyethylene ether macromonomer A, small monomer B containing carboxyl and vinyl, functional monomer C1 containing phosphoric acid group and vinyl, and functional monomer C2 containing quaternary ammonium group, sulfonic acid group and vinyl.

[0034] The weight average molecular weight Mw of the ethylene glycol monovinyl ether polyoxyethylene ether macromonomer A is 3000-6000.

[0035] The small monomer B containing carboxyl and vinyl includes any one of acrylic acid, methacrylic acid, hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxyethyl methacrylate and hydroxypropyl methacrylate.

[0036] The functional monomer C1 containing both phosphoric acid group and vinyl group is 2-(methacryloyloxy)ethyl phosphate and / or 10-(2-methacryloyloxy)phosphonic acid monodecyl ester.

[0037] 1. The structure of the functional monomer C2 containing both quaternary ammonium group, sulfonic acid group and vinyl group is as follows:

[0038] R1 in the structure of C2 is -H or -CH3; R2 in the structure of C2 is any one of -CH2-, -CH2CH2-, -CH2CH2CH2-, -CH2CH2CH2CH2- 、 -CH2CH2CH2CH2CH2-; R3 in the structure of C2 is any one of -CH2-, -CH2CH2-, -CH2CH2CH2-, -CH2CH2CH2CH2- 、 -CH2CH2CH2CH2CH2-. Preferably, R2 in the structure of C2 is -CH2CH2CH3; R3 in the structure of C2 is -CH2CH2CH2- or -CH2CH2CH2CH2-. Specifically, the functional monomer C2 containing both quaternary ammonium group, sulfonic acid group and vinyl group is 3-[(3-acrylamidopropyl)dimethylammonio]propane-1-sulfonate and / or 4-[(3-methacrylamidopropyl)dimethylammonio]butane-1-sulfonate.

[0039] The molar ratio of the ethylene glycol monovinyl ether polyoxyethylene ether macromonomer A to the small monomer B containing both carboxyl group and vinyl group is 1:(3.5-4.25). The molar ratio of the ethylene glycol monovinyl ether polyoxyethylene ether macromonomer A to the functional monomer C1 containing both phosphoric acid group and vinyl group, the functional monomer C2 containing both quaternary ammonium group, sulfonic acid group and vinyl group is 1:(0.05-0.15):(0.10-0.20). Preferably, the molar ratio of the ethylene glycol monovinyl ether polyoxyethylene ether macromonomer A to the small monomer B containing both carboxyl group and vinyl group, the functional monomer C1 containing both phosphoric acid group and vinyl group, the functional monomer C2 containing both quaternary ammonium group, sulfonic acid group and vinyl group is 1:4:0.10:0.15.

[0040] A preparation method of an anti-mud polycarboxylate superplasticizer, comprising the following steps:

[0041] Step one, 10 parts by weight of ethylene glycol monovinyl ether polyoxyethylene ether macromonomer A is fully dissolved in 10-20 parts of deionized water to obtain a macromonomer A aqueous solution;

[0042] Meanwhile, an initiator aqueous solution is prepared: 1-2 parts by weight of ascorbic acid is fully dissolved in 18-19 parts by weight of deionized water to obtain an initiator aqueous solution;

[0043] Meanwhile, prepare the aqueous solution of small monomer B: dissolve 10 parts by weight of small monomer B containing carboxyl and vinyl, 0.25-2 parts by weight of hydrogen peroxide, and 0.5-2 parts by weight of mercaptoethanol in 20 parts by weight of deionized water to obtain the aqueous solution of small monomer B;

[0044] Meanwhile, prepare the aqueous solution of functional monomer C1: dissolve 10 parts by weight of functional monomer C1 containing phosphonic acid group and vinyl, 0.25-2 parts by weight of hydrogen peroxide, 0.25-1 part by weight of ammonium persulfate, and 0.5-2 parts by weight of mercaptoethanol in 20 parts by weight of deionized water to obtain the aqueous solution of functional monomer C1;

[0045] Meanwhile, prepare the aqueous solution of functional monomer C2: dissolve 10 parts by weight of functional monomer C2 containing quaternary ammonium group, sulfonic acid group, and vinyl, 0.25-1 part by weight of hydrogen peroxide, 0.25-1 part by weight of ammonium persulfate, and 0.5-2 parts by weight of mercaptoethanol in 20 parts by weight of deionized water to obtain the aqueous solution of functional monomer C2;

[0046] Step two, control the temperature of the aqueous solution of large monomer A to be 20-40°C by water bath heating, and simultaneously add the aqueous solution of initiator, the aqueous solution of small monomer B, the aqueous solution of functional monomer C1, and the aqueous solution of functional monomer C2 into the aqueous solution of monomer A at a rotation speed of 100-250 rpm. The molar ratio of the aqueous solution of ethylene glycol monovinyl ether polyoxyethylene ether large monomer A to the aqueous solution of small monomer B containing carboxyl and vinyl in the aqueous solution of functional monomer C1, and the aqueous solution of functional monomer C2 is 1:(3.5-4.25):(0.05-0.15):(0.10-0.20). The time for adding the aqueous solution of initiator, the aqueous solution of small monomer B, the aqueous solution of functional monomer C1, and the aqueous solution of functional monomer C2 is uniformly 30-60 minutes. After the addition is completed, the reaction is maintained at 20-40°C for 15-30 minutes. After cooling to room temperature, 0.1-0.5 mol / L of aqueous sodium hydroxide solution is added to adjust the pH value of the system to 6-8, and the anti-mud polycarboxylate superplasticizer is obtained.

[0047] Example 1: The anti-mud polycarboxylate superplasticizer is prepared from ethylene glycol monovinyl ether polyoxyethylene ether large monomer (EPEG, Mw=3000, provided by Sanjiang Chemical Co., Ltd.), acrylic acid AA (CAS: 79-10-7, molecular weight 72.063), 10-(2-methacryloyloxy) phosphonic acid monodecyl ester (molecular weight 322.334, CAS: 85590-00-7), and 3-[(3-acrylamidopropyl)dimethylammonio]propane-1-sulfonate (molecular weight 278.37, CAS: 80293-60-3) at a molar ratio of 1:4:0.10:0.15.

[0048] A preparation method of an anti-mud polycarboxylic acid water reducer, comprising the following steps:

[0049] Step one, 10 parts by weight of ethylene glycol monovinyl ether polyoxyethylene ether macromonomer (EPEGMw=3000, provided by Sanjiang Chemical Co., Ltd.) is fully dissolved in 20 parts of deionized water to obtain an EPEG macromonomer aqueous solution;

[0050] Meanwhile, an initiator aqueous solution is prepared: 1.5 parts by weight of ascorbic acid VC (CAS: 50-81-7, molecular weight 176.124) is fully dissolved in 18.5 parts by weight of deionized water to obtain an initiator aqueous solution;

[0051] Meanwhile, an aqueous solution of small monomer B is prepared: 10 parts by weight of acrylic acid AA (CAS: 79-10-7, molecular weight 72.063), 0.5 parts by weight of hydrogen peroxide, and 1.5 parts by weight of mercaptoethanol are fully dissolved in 20 parts by weight of deionized water to obtain an aqueous solution of acrylic acid;

[0052] Meanwhile, a functional monomer C1 aqueous solution is prepared: 10 parts by weight of 10-(2-methacryloyloxy) phosphoric acid monodecyl ester (CAS: 85590-00-7), 0.5 parts by weight of hydrogen peroxide (CAS: 7722-84-1), 1 part by weight of ammonium persulfate (CAS: 7727-54-0), and 1.5 parts by weight of mercaptoethanol are fully dissolved in 20 parts by weight of deionized water to obtain a functional monomer C1 aqueous solution;

[0053] Meanwhile, a functional monomer C2 aqueous solution is prepared: 10 parts by weight of 3-[(3-acrylamidopropyl)dimethylammonio]propane-1-sulfonate (molecular weight 278.37, CAS: 80293-60-3), 0.25-1 parts by weight of hydrogen peroxide (CAS: 7722-84-1), 0.25-1 parts by weight of ammonium persulfate (CAS: 7727-54-0), and 0.5-2 parts by weight of mercaptoethanol (CAS: 60-24-2, molecular weight: 78.133) are fully dissolved in 20 parts by weight of deionized water to obtain a functional monomer C2 aqueous solution;

[0054] Step two, the temperature of EPEG macromonomer aqueous solution is controlled by water bath heating at 25℃, the initiator aqueous solution, acrylic acid aqueous solution, functional monomer C1 aqueous solution, functional monomer C2 aqueous solution are simultaneously added into the EPEG macromonomer aqueous solution at a speed of 120 rpm, the molar ratio of ethylene glycol monovinyl ether polyoxyethylene ether macromonomer EPEG in the EPEG macromonomer aqueous solution, acrylic acid AA in the acrylic acid aqueous solution, 10-(2-methyl acryloyl oxy) phosphoric acid monodecyl ester in the functional monomer C1 aqueous solution, 3-[(3-acrylamidopropyl) dimethyl ammonium] propane-1-sulfonate in the functional monomer C2 aqueous solution is 1:4:0.10:0.15, the dropping time of the initiator aqueous solution, monomer B aqueous solution, functional monomer C1 aqueous solution, functional monomer C2 aqueous solution is 30 minutes, after the dropping is completed, the reaction is maintained at 25℃ for 15 minutes, then the system is cooled to room temperature, 0.2 mol / L sodium hydroxide aqueous solution is added, the pH value of the system is adjusted to 8, then the anti-mud polycarboxylate superplasticizer is obtained.

[0055] The difference between example 2 and example 1 is that the anti-mud polycarboxylate superplasticizer is made of ethylene glycol monovinyl ether polyoxyethylene ether macromonomer EPEG (Mw=3000), acrylic acid AA, 10-(2-methyl acryloyl oxy) phosphoric acid monodecyl ester, 3-[(3-acrylamidopropyl) dimethyl ammonium] propane-1-sulfonate in a molar ratio of 1:3.5:0.10:0.15.

[0056] The difference between example 3 and example 1 is that the anti-mud polycarboxylate superplasticizer is made of ethylene glycol monovinyl ether polyoxyethylene ether macromonomer EPEG (Mw=3000), acrylic acid AA, 10-(2-methyl acryloyl oxy) phosphoric acid monodecyl ester, 3-[(3-acrylamidopropyl) dimethyl ammonium] propane-1-sulfonate in a molar ratio of 1:3.75:0.10:0.15.

[0057] The difference between example 4 and example 1 is that the anti-mud polycarboxylate superplasticizer is made of ethylene glycol monovinyl ether polyoxyethylene ether macromonomer EPEG (Mw=3000), acrylic acid AA, 10-(2-methyl acryloyl oxy) phosphoric acid monodecyl ester, 3-[(3-acrylamidopropyl) dimethyl ammonium] propane-1-sulfonate in a molar ratio of 1:4.25:0.10:0.15.

[0058] The difference between example 5 and example 1 is that the anti-mud polycarboxylate superplasticizer is made of ethylene glycol monovinyl ether polyoxyethylene ether macromonomer EPEG (Mw=3000), acrylic acid AA, 10-(2-methyl acryloyl oxy) phosphoric acid monodecyl ester, 3-[(3-acrylamidopropyl) dimethyl ammonium] propane-1-sulfonate in a molar ratio of 1:4:0.05:0.15.

[0059] Example 6 differs from Example 1 in that the anti-slump polycarboxylate superplasticizer is made from ethylene glycol monovinyl ether polyoxyethylene ether macromonomer EPEG (Mw=3000), acrylic acid AA, 10-(2-methacryloyloxy)phosphonic acid monodecyl ester, 3-[(3-acrylamidopropyl)dimethylammonio]propane-1 -sulfonate in a molar ratio of 1 :4:0.15:0.15.

[0060] Example 7 differs from Example 1 in that the anti-slump polycarboxylate superplasticizer is made from ethylene glycol monovinyl ether polyoxyethylene ether macromonomer EPEG (Mw=3000), acrylic acid AA, 10-(2-methacryloyloxy)phosphonic acid monodecyl ester, 3-[(3-acrylamidopropyl)dimethylammonio]propane-1 -sulfonate in a molar ratio of 1 :4:0.10:0.10.

[0061] Example 8 differs from Example 1 in that the anti-slump polycarboxylate superplasticizer is made from ethylene glycol monovinyl ether polyoxyethylene ether macromonomer EPEG (Mw=3000), acrylic acid AA, 10-(2-methacryloyloxy)phosphonic acid monodecyl ester, 3-[(3-acrylamidopropyl)dimethylammonio]propane-1 -sulfonate in a molar ratio of 1 :4:0.10:0.20.

[0062] Example 9 differs from Example 1 in that the anti-slump polycarboxylate superplasticizer is made from ethylene glycol monovinyl ether polyoxyethylene ether macromonomer (EPEG, Mw=3000, provided by Sanjiang Chemical Co., Ltd.), methacrylic acid MMA (CAS: 79-41-4, molecular weight: 86.089), 10-(2-methacryloyloxy)phosphonic acid monodecyl ester (molecular weight 322.334, CAS: 85590-00-7), 3-[(3-acrylamidopropyl)dimethylammonio]propane-1 -sulfonate (molecular weight 278.37, CAS: 80293-60-3) in a molar ratio of 1 :4:0.10:0.15.

[0063] Example 10 differs from Example 1 in that the anti-slump polycarboxylate superplasticizer is made from ethylene glycol monovinyl ether polyoxyethylene ether macromonomer (EPEG, Mw=3000, provided by Sanjiang Chemical Co., Ltd.), methacrylic acid MMA (CAS: 79-41-4, molecular weight: 86.089), 10-(2-methacryloyloxy)phosphonic acid monodecyl ester (molecular weight 322.334, CAS: 85590-00-7), 4-[(3-methacrylamidopropyl)dimethylammonio]butane-1 -sulfonate (CAS: 83623-32-9, molecular weight: 306.42) in a molar ratio of 1 :4:0.10:0.15.

[0064] The difference between Comparative Example 1 and Example 1 is that the polycarboxylate superplasticizer is made of ethylene glycol monovinyl ether polyoxyethylene ether macromonomer EPEG (Mw=3000) and acrylic acid AA in a molar ratio of 1:4.

[0065] The preparation method of the polycarboxylate superplasticizer comprises the following steps:

[0066] In step one, 10 parts by weight of ethylene glycol monovinyl ether polyoxyethylene ether macromonomer (EPEG Mw=3000, provided by Sanjiang Chemical Co., Ltd.) is fully dissolved in 20 parts of deionized water to obtain an EPEG macromonomer aqueous solution;

[0067] Meanwhile, an initiator aqueous solution is prepared: 1.5 parts by weight of ascorbic acid VC (CAS: 50-81-7, molecular weight 176.124) is fully dissolved in 18.5 parts by weight of deionized water to obtain an initiator aqueous solution;

[0068] Meanwhile, a small monomer B aqueous solution is prepared: 10 parts by weight of acrylic acid AA (CAS: 79-10-7, molecular weight 72.063), 0.5 parts by weight of hydrogen peroxide, and 1.5 parts by weight of mercaptoethanol are fully dissolved in 20 parts by weight of deionized water to obtain an acrylic acid aqueous solution;

[0069] In step two, the temperature of the EPEG macromonomer aqueous solution is controlled to be 25°C by water bath heating, and the initiator aqueous solution and the acrylic acid aqueous solution are simultaneously added to the EPEG macromonomer aqueous solution at a speed of 120 rpm. The molar ratio of ethylene glycol monovinyl ether polyoxyethylene ether macromonomer EPEG in the EPEG macromonomer aqueous solution to acrylic acid AA in the acrylic acid aqueous solution is 1:4. The addition of the initiator aqueous solution and the acrylic acid aqueous solution is completed uniformly in 30 minutes. After the addition is completed, the reaction is maintained at 25°C for 15 minutes. After cooling to room temperature, 0.2 mol / L sodium hydroxide aqueous solution is added to adjust the pH value of the system to 8 to obtain the polycarboxylate superplasticizer.

[0070] The difference between Comparative Example 2 and Example 1 is that the anti-mud polycarboxylate superplasticizer is made of ethylene glycol monovinyl ether polyoxyethylene ether macromonomer EPEG (Mw=3000), acrylic acid AA, 10-(2-methyl acryloyloxy) phosphoric acid monodecyl ester, and 3-[(3-acrylamidopropyl) dimethylammonio] propane-1-sulfonate in a molar ratio of 1:3:0.10:0.15.

[0071] The difference between Comparative Example 3 and Example 1 is that the anti-mud polycarboxylate superplasticizer is made of ethylene glycol monovinyl ether polyoxyethylene ether macromonomer EPEG (Mw=3000), acrylic acid AA, 10-(2-methyl acryloyloxy) phosphoric acid monodecyl ester, and 3-[(3-acrylamidopropyl) dimethylammonio] propane-1-sulfonate in a molar ratio of 1:5:0.10:0.15.

[0072] Comparative Example 4 differs from Example 1 in that the anti-slump polycarboxylate water reducer is made from ethylene glycol monovinyl ether polyoxyethylene ether macromonomer EPEG (Mw = 3000), acrylic acid AA, 3-[(3-acrylamidopropyl)dimethylammonio]propane-1 -sulfonate in a molar ratio of 1 :4:0.15.

[0073] Comparative Example 5 differs from Example 1 in that the anti-slump polycarboxylate water reducer is made from ethylene glycol monovinyl ether polyoxyethylene ether macromonomer EPEG (Mw = 3000), acrylic acid AA, 10-(2-methacryloyloxy)phosphate monodecyl ester, 3-[(3-acrylamidopropyl)dimethylammonio]propane-1 -sulfonate in a molar ratio of 1 :4:0.025:0.15.

[0074] Comparative Example 6 differs from Example 1 in that the anti-slump polycarboxylate water reducer is made from ethylene glycol monovinyl ether polyoxyethylene ether macromonomer EPEG (Mw = 3000), acrylic acid AA, 10-(2-methacryloyloxy)phosphate monodecyl ester, 3-[(3-acrylamidopropyl)dimethylammonio]propane-1 -sulfonate in a molar ratio of 1 :4:0.20:0.15.

[0075] Comparative Example 7 differs from Example 1 in that the anti-slump polycarboxylate water reducer is made from ethylene glycol monovinyl ether polyoxyethylene ether macromonomer EPEG (Mw = 3000), acrylic acid AA, 10-(2-methacryloyloxy)phosphate monodecyl ester in a molar ratio of 1 :4:0.10.

[0076] Comparative Example 8 differs from Example 1 in that the anti-slump polycarboxylate water reducer is made from ethylene glycol monovinyl ether polyoxyethylene ether macromonomer EPEG (Mw = 3000), acrylic acid AA, 10-(2-methacryloyloxy)phosphate monodecyl ester, 3-[(3-acrylamidopropyl)dimethylammonio]propane-1 -sulfonate in a molar ratio of 1 :4:0.10:0.05.

[0077] Comparative Example 9 differs from Example 1 in that the anti-slump polycarboxylate water reducer is made from ethylene glycol monovinyl ether polyoxyethylene ether macromonomer EPEG (Mw = 3000), acrylic acid AA, 10-(2-methacryloyloxy)phosphate monodecyl ester, 3-[(3-acrylamidopropyl)dimethylammonio]propane-1 -sulfonate in a molar ratio of 1 :4:0.10:0.25.

[0078] Performance test 1: The polycarboxylate superplasticizer mother liquor is diluted to 1.1‰ for cement paste application experiment, according to the cement paste fluidity test method in GB / T8077-2023. Specifically, in the cement paste mixer, the reference cement

PO42.5 Portland cement (rotary kiln), provided by Shandong Lucheng Cement Co., Ltd.

[0079] Performance test 2: The water-reducing rate is tested according to the method recorded in GB / T8076-2016 “Concrete Admixtures Standard” and GB / T8077-2012 “Concrete Admixtures Homogeneity Test Method” “14 Cement Mortar Water-reducing Rate”.

[0080] Performance test 3: The early compressive strength is tested according to GB / T 17671-2020 “Cement Mortar Strength Test Method”. The concrete formula is: 450 parts by weight of PO42.5 Portland cement, 1350 parts by weight of standard sand, and the water-reducing agent solid content is 0.2wt% of the cement dosage. The mortar age is calculated from the mixing of cement and water, and the sample is taken out from the constant temperature and humidity box for testing the compressive strength after three days (3d) and seven days (7d) of hydration.

[0081] Table 1: Test parameter table of polycarboxylate superplasticizer in examples 1-10 and comparative examples 1-9

[0082] Initial net slurry (mm) Net slurry over time (mm) Water reduction rate (%) Early compressive strength (3d) MPa Early compressive strength (7d) MPa Example 1 233 219 27.1 20.15 34.64 Example 2 223 209 26.3 19.24 32.79 Example 3 229 216 26.8 20.01 34.39 Example 4 225 211 25.9 19.67 33.76 Example 5 226 210 25.9 19.51 33.28 Example 6 235 219 26.8 19.95 34.05 Example 7 221 204 26.1 18.96 32.24 Example 8 234 218 27.5 20.29 34.76 Example 9 228 224 26.4 19.65 33.82 Example 10 230 216 26.8 19.83 33.96 Comparative Example 1 189 171 24.8 16.95 30.08 Comparative Example 2 215 192 25.6 17.92 30.82 Comparative Example 3 213 195 25.3 18.37 31.26 Comparative Example 4 204 187 25.2 17.46 30.57 Comparative Example 5 210 193 25.5 17.61 30.75 Comparative Example 6 233 216 26.5 19.87 33.89 Comparative Example 7 198 182 25.3 17.29 30.43 Comparative Example 8 216 191 25.6 18.09 31.05 Comparative Example 9 229 212 26.9 19.85 33.78

[0083] It can be seen from examples 1-4 and comparative examples 1 in combination with table 1 that the polycarboxylate superplasticizer prepared from ethylene glycol monovinyl ether polyoxyethylene ether macromonomer EPEG, acrylic acid AA, 10-(2-methyl acryloyloxy) phosphoric acid monodecyl ester and 3-[(3-acrylamidopropyl) dimethylammonio] propane-1-sulfonate has high initial paste value and paste over time value, and has good dispersion and adsorption performance and clay resistance.

[0084] It can be seen from the combination of Examples 1-4 and Comparative Examples 1-3 and Table 1 that the molar ratio of ethylene glycol monovinyl ether polyoxyethylene ether macromonomer EPEG, acrylic acid AA, 10-(2-methacryloyloxy) monodecyl phosphate, and 3-[(3-acrylamidopropyl) dimethylammonio] propane-1-sulfonate is controlled to be 1:(3.5-4.25):0.10:0.15, and the prepared polycarboxylic acid water reducing agent has excellent dispersion adsorption performance and clay resistance.

[0085] It can be seen from the combination of Examples 1, Examples 5-6 and Comparative Examples 4-6 and Table 1 that the molar ratio of ethylene glycol monovinyl ether polyoxyethylene ether macromonomer EPEG, acrylic acid AA, 10-(2-methacryloyloxy) monodecyl phosphate, and 3-[(3-acrylamidopropyl) dimethylammonio] propane-1-sulfonate is controlled to be 1:4:(0.05-0.20):0.15, and the prepared polycarboxylic acid water reducing agent has excellent dispersion adsorption performance and clay resistance. If the amount of 10-(2-methacryloyloxy) monodecyl phosphate is too low, the effect on dispersion adsorption performance and clay resistance is relatively insignificant. If the amount of 10-(2-methacryloyloxy) monodecyl phosphate is too high, it will affect the dispersion adsorption performance and clay resistance of the polycarboxylic acid water reducing agent and also lead to a higher production cost.

[0086] It can be seen from the combination of Examples 1, Examples 7-8 and Comparative Examples 7-9 and Table 1 that the molar ratio of ethylene glycol monovinyl ether polyoxyethylene ether macromonomer EPEG, acrylic acid AA, 10-(2-methacryloyloxy) monodecyl phosphate, and 3-[(3-acrylamidopropyl) dimethylammonio] propane-1-sulfonate is controlled to be 1:4:0.10:(0.10-0.20), and the prepared polycarboxylic acid water reducing agent has excellent dispersion adsorption performance and clay resistance. If the amount of 3-[(3-acrylamidopropyl) dimethylammonio] propane-1-sulfonate is too low, the effect on dispersion adsorption performance and clay resistance is relatively insignificant. If the amount of 3-[(3-acrylamidopropyl) dimethylammonio] propane-1-sulfonate is too high, it will have a negative impact on the performance and also increase the overall production cost.

[0087] In summary, the molar ratio of ethylene glycol monovinyl ether polyoxyethylene ether macromonomer EPEG, acrylic acid AA, 10-(2-methacryloyloxy) monodecyl phosphate, and 3-[(3-acrylamidopropyl) dimethylammonio] propane-1-sulfonate is controlled to be 1:(3.5-4.25):(0.05-0.20):(0.10-0.20), i.e., by introducing phosphate groups, quaternary ammonium salt groups, and sulfonic acid groups into the structure of the polycarboxylic acid water reducing agent, it is easier for it to be adsorbed on the surface of clay rather than being embedded in the layered structure of clay, thereby improving the dispersibility, adsorbability, and clay resistance of the polycarboxylic acid water reducing agent and facilitating the improvement of the early strength performance of concrete.

[0088] It should be noted that the specific embodiments are only used to explain and describe the technical solutions of the present application, and are not used to limit the present application. Those skilled in the art can make modifications to the embodiments without creative contribution as long as the modifications are within the scope of the present application.

Claims

1. An anti-mud polycarboxylate water reducer, characterized by: The anti-slurry polycarboxylic acid water reducing agent comprises an ethylene glycol monovinyl ether polyoxyethylene ether macromonomer A, a small monomer B containing carboxyl and vinyl groups, a functional monomer C1 containing phosphoric acid groups and vinyl groups, and a functional monomer C2 containing quaternary ammonium groups, sulfonic acid groups and vinyl groups. 2.The anti-mud polycarboxylate water reducer according to claim 1, characterized in that: The functional monomer C2 containing quaternary ammonium groups, sulfonic acid groups and vinyl groups has the following structural formula: R1 is -H or -CH3; R2 is -CH2-, -CH2CH2-, -CH2CH2CH2-, -CH2CH2CH2CH2- 、 -CH2CH2CH2CH2CH2-; R3 is -CH2-, -CH2CH2-, -CH2CH2CH2-, -CH2CH2CH2CH2- 、 -CH2CH2CH2CH2CH2-. 3.The anti-mud polycarboxylate water reducer according to claim 2, characterized in that: In the structural formula of C2, R2 is -CH2CH2CH3; and R3 is -CH2CH2CH2- or -CH2CH2CH2CH2-. 4.The anti-mud polycarboxylate water reducer according to claim 1, characterized in that: The molar ratio of the ethylene glycol monovinyl ether polyoxyethylene ether macromonomer A to the small monomer B containing carboxyl and vinyl groups is 1:(3.5-4.25).

5. The anti-mud polycarboxylate superplasticizer according to claim 4, characterized in that: The molar ratio of the ethylene glycol monovinyl ether polyoxyethylene ether macromonomer A to the functional monomer C1 containing phosphoric acid groups and vinyl groups and the functional monomer C2 containing quaternary ammonium groups, sulfonic acid groups and vinyl groups is 1:(0.05-0.15):(0.10-0.20). 6.The anti-mud polycarboxylate water reducer according to claim 5, characterized in that: The molar ratio of the ethylene glycol monovinyl ether polyoxyethylene ether macromonomer A to the small monomer B containing carboxyl and vinyl groups, the functional monomer C1 containing phosphoric acid groups and vinyl groups, and the functional monomer C2 containing quaternary ammonium groups, sulfonic acid groups and vinyl groups is 1:4:0.10:0.

15.

7. The anti-mud polycarboxylate superplasticizer according to claim 6, characterized in that: The weight average molecular weight Mw of the ethylene glycol monovinyl ether polyoxyethylene ether macromonomer A is 3000-6000. 8.The anti-mud polycarboxylate water reducer according to claim 7, characterized in that: The functional monomer C2 containing quaternary ammonium groups, sulfonic acid groups and vinyl groups is 3-[(3-acrylamidopropyl)dimethylammonio]propane-1-sulfonate and / or 4-[(3-methacrylamidopropyl)dimethylammonio]butane-1-sulfonate; the functional monomer C1 containing phosphoric acid groups and vinyl groups is 10-(2-methacryloyloxy)phosphonic acid monodecyl ester; and the small monomer B containing carboxyl and vinyl groups is acrylic acid and / or methacrylic acid.

9. A method for preparing the anti-slump polycarboxylate water reducer according to any one of claims 1-8, characterized by: The method comprises the following steps: Step one, 10 parts by weight of the ethylene glycol monovinyl ether polyoxyethylene ether macromonomer A is fully dissolved in 10-20 parts of deionized water to obtain a macromonomer A aqueous solution; An initiator aqueous solution is prepared at the same time: 1-2 parts by weight of ascorbic acid is fully dissolved in 18-19 parts by weight of deionized water to obtain an initiator aqueous solution; A small monomer B aqueous solution is prepared at the same time: 10 parts by weight of the small monomer B containing carboxyl and vinyl groups, 0.25-2 parts by weight of hydrogen peroxide, and 0.5-2 parts by weight of mercaptoethanol are fully dissolved in 20 parts by weight of deionized water to obtain a small monomer B aqueous solution; Meanwhile, the functional monomer C1 aqueous solution is prepared: 10 parts by weight of the functional monomer C1 containing both phosphoric acid group and vinyl group, 0.25-2 parts by weight of hydrogen peroxide, 0.25-1 part by weight of ammonium persulfate, and 0.5-2 parts by weight of mercaptoethanol are dissolved in 20 parts by weight of deionized water to obtain the functional monomer C1 aqueous solution; Meanwhile, the functional monomer C2 aqueous solution is prepared: 10 parts by weight of the functional monomer C2 containing both quaternary ammonium group, sulfonic acid group and vinyl group, 0.25-1 part by weight of hydrogen peroxide, 0.25-1 part by weight of ammonium persulfate, and 0.5-2 parts by weight of mercaptoethanol are dissolved in 20 parts by weight of deionized water to obtain the functional monomer C2 aqueous solution; In step two, the temperature of the macromonomer A aqueous solution is controlled by water bath heating to be 20-40℃, and the initiator aqueous solution, the small monomer B aqueous solution, the functional monomer C1 aqueous solution, and the functional monomer C2 aqueous solution are simultaneously added dropwise to the macromonomer A aqueous solution at a speed of 100-250 rpm. After the dropwise addition is completed, the reaction is maintained at 20-40℃ for 15-30 min, and then 0.1-0.5 mol / L sodium hydroxide aqueous solution is added to adjust the pH value of the system to 6-8, thereby obtaining the anti-mud polycarboxylic acid water reducer.

10. The method of claim 9, wherein: In step two, the molar ratio of the ethylene glycol monovinyl ether polyoxyethylene ether macromonomer A in the macromonomer A aqueous solution, the small monomer B containing both carboxyl and vinyl group in the small monomer B aqueous solution, the functional monomer C1 containing both phosphoric acid group and vinyl group in the functional monomer C1 aqueous solution, and the functional monomer C2 containing both quaternary ammonium group, sulfonic acid group and vinyl group in the functional monomer C2 aqueous solution is 1:(3.5-4.25):(0.05-0.15):(0.10-0.20), and the dropwise addition of the initiator aqueous solution, the small monomer B aqueous solution, the functional monomer C1 aqueous solution, and the functional monomer C2 aqueous solution is completed uniformly in 30-60 min.