Anti-mud monomer and preparation method thereof, and anti-mud water reducer and preparation method thereof

Abstract

The invention relates to an anti-mud monomer and a preparation method thereof, and an anti-mud water reducer and a preparation method thereof. The anti-mud monomer comprises the following components in parts by weight: 20-30 parts of unsaturated phosphoric acid; 30-50 parts of an unsaturated quaternary ammonium salt monomer; 0.1 to 0.4 part of a first oxidant; 0.1 to 0.4 part of a first reducing agent; and water. The water reducing agent provided by the invention contains a phosphate group and a quaternary ammonium salt group, and the phosphate group provides strong complexing ability to calcium ions, so that the dispersity is enhanced; the quaternary ammonium salt group improves the compatibility with clay minerals, so that the mud resistance is remarkably improved; and the two are combined with a flexible side chain of a polyether macromonomer (TPEG) long chain to form a multifunctional synergistic effect, so that the complex environment requirements are met.

Description

Technical Field

[0001] The invention relates to the technical field of concrete admixtures, in particular to an anti-mud monomer and a preparation method thereof, an anti-mud type water reducing agent and a preparation method thereof. Background Art

[0002] In modern concrete construction, polycarboxylate water-reducing agent has become a key component of concrete admixtures due to its excellent water-reducing performance and environmental protection characteristics, and is widely used in various projects. However, when high-clay mineral components such as bentonite and laterite are added to the raw materials of concrete, the performance of traditional polycarboxylate water-reducing agent is often significantly affected. This is mainly because the layered silicates (such as montmorillonite, etc.) contained in high-clay minerals have a large specific surface area and strong adsorption, which can easily over-absorb the effective molecules of polycarboxylate water-reducing agent, thereby weakening its dispersion effect on the surface of cement particles. This phenomenon usually causes problems such as slump loss and deterioration of working performance, which seriously affects the construction performance and engineering quality of concrete. Summary of the invention

[0003] Based on this, it is necessary to provide an anti-mud monomer and a preparation method thereof, an anti-mud type water reducer and a preparation method thereof.

[0004] To achieve the above object, the present invention provides a technical solution:

[0005] The present invention provides an anti-mud monomer, which comprises, by weight:

[0006]

[0007] In some embodiments, the unsaturated phosphoric acid includes at least one of methacryloyloxyethyl phosphoric acid and triethoxy phosphoric acid.

[0008] In some embodiments, the unsaturated quaternary ammonium salt monomer includes at least one of acrylamidopropyl trimethyl ammonium chloride, methacryloyloxyethyl trimethyl ammonium chloride, acryloyloxyethyl trimethyl ammonium chloride and methacryloyloxypropyl trimethyl ammonium chloride.

[0009] In some embodiments, the acrylamidopropyltrimethylammonium chloride is a 50 wt. % aqueous solution.

[0010] In some embodiments, the first oxidant includes at least one of potassium persulfate, hydrogen peroxide and ammonium persulfate.

[0011] In some embodiments, the first reducing agent includes at least one of sodium bisulfite, sodium hypophosphite, sodium thiosulfate and vitamin C.

[0012] In some embodiments, the mass fraction of water is 30-60 parts.

[0013] In some embodiments, the water is deionized water.

[0014] The present invention provides a method for preparing an anti-mud monomer, comprising the steps of:

[0015] Mixing unsaturated phosphoric acid, unsaturated quaternary ammonium salt monomer and water to obtain a mixed solution;

[0016] The oxidizing agent aqueous solution and the reducing agent aqueous solution are added dropwise to the mixed solution, and after the addition is completed, the mixture is kept warm for reaction to obtain the anti-mud monomer.

[0017] In some embodiments, an aqueous oxidant solution and an aqueous reductant solution are simultaneously added dropwise to the mixed solution.

[0018] In some embodiments, the dripping time of the aqueous oxidant solution is 1 to 3 hours, preferably 1 hour.

[0019] In some embodiments, the reducing agent aqueous solution is added dropwise for 1 to 3 hours, preferably 1 hour.

[0020] In some embodiments, the reaction temperature of the insulation reaction is 60°C to 90°C, preferably 70°C.

[0021] In some embodiments, the reaction time of the insulation reaction is 1.5 h to 3 h, preferably 2 h.

[0022] The present invention provides an anti-mud type water reducing agent, which comprises, by weight:

[0023]

[0024] In some embodiments, the unsaturated polyether includes at least one of ethylene glycol monovinyl ether, 4-hydroxybutyl vinyl ether and butanediol monovinyl polyethylene glycol ether.

[0025] In some embodiments, the unsaturated acid includes at least one of acrylic acid and methacrylic acid, preferably acrylic acid.

[0026] In some embodiments, the oxidant includes at least one of hydrogen peroxide, ammonium persulfate and potassium persulfate, preferably hydrogen peroxide.

[0027] In some embodiments, the reducing agent includes at least one of sodium sulfite, sodium hypophosphite and sodium thiosulfate, preferably sodium hypophosphite.

[0028] In some embodiments, the chain transfer agent includes thioglycolic acid, sodium bisulfite, mercaptoethanol, and mercaptopropionic acid, preferably thioglycolic acid.

[0029] In some embodiments, the mass fraction of water is 160-200 parts.

[0030] In some embodiments, the raw materials for preparing the air entraining monomer include, by weight:

[0031] 30-80 parts of Malay rosin;

[0032] 20-30 parts of acylating agent;

[0033] 20-30 parts of catalyst;

[0034] In some embodiments, the catalyst includes at least one of triethylamine, diisopropylethylamine and sodium carbonate.

[0035] In some embodiments, the acylating agent includes at least one of methacryloyl chloride and acryloyl chloride.

[0036] In some embodiments, the steps of preparing the air entraining monomer include:

[0037] S110, dissolving maleic rosin in a solvent to obtain a maleic rosin solution;

[0038] S120, adding a mixed solution of a catalyst and an acylating agent dropwise to the maleic rosin solution, stirring to react after the addition is completed, and obtaining the air-entraining monomer after the reaction is completed.

[0039] In some embodiments, in step S120, a mixed solution of the catalyst and the acylating agent is added dropwise in an ice bath at a temperature of 0°C-5°C.

[0040] In some embodiments, in step S120, the time for adding the mixed solution of the catalyst and the acylating agent dropwise is 1 h to 3 h, preferably 1 h.

[0041] In some embodiments, in step S120, the stirring reaction temperature is 20°C to 30°C.

[0042] In some embodiments, in step S120, the stirring reaction time is 3 h to 6 h, preferably 4 h.

[0043] In some embodiments, in step S120, the mixed solution containing the gas-entraining monomer obtained after the reaction is washed three times with deionized water, the organic phase is separated and dried with anhydrous sodium sulfate, and the solvent is removed by rotary evaporation.

[0044] In some embodiments, the solvent comprises dichloromethane.

[0045] In some embodiments, the amount of the solvent used is 90-150 parts by weight.

[0046] The present invention provides a method for preparing an anti-mud type water reducing agent, comprising the steps of:

[0047] S210, mixing an air entraining monomer, an unsaturated polyether, an unsaturated acid, a second oxidant and water to obtain a mother liquor;

[0048] S220, adding liquid A and liquid B dropwise to the mother liquor, and continuing the heat preservation reaction for 0.5 to 1.5 hours after the addition is completed, and adjusting the pH value of the solution to 7 to 8 after the reaction is completed, so as to obtain the anti-mud type water reducing agent;

[0049] Wherein, liquid A is a mixture of unsaturated acid, anti-mud monomer and water, and the mass ratio of the unsaturated acid in liquid A to the unsaturated acid in the mother liquor is: (10-15):15;

[0050] Liquid B is an aqueous solution of a second reducing agent and a chain transfer agent.

[0051] In some embodiments, in step S220, the dropwise addition time of liquid A is 1 to 3 hours, and the dropwise addition time of liquid B is 1 to 3 hours.

[0052] In some embodiments, by weight, in step S220, 2 to 5 parts of alkaline solution are added to adjust the pH value to 7 to 8.

[0053] In some embodiments, the alkali solution includes 30 wt. % sodium hydroxide.

[0054] Beneficial effects of the present invention:

[0055] This patent introduces a rosin skeleton into the main chain molecule of the polycarboxylate water reducer to enhance the adsorption capacity of the water reducer on the surface of cement particles.

[0056] The water reducer provided by this patent contains phosphoric acid groups and quaternary ammonium salt groups. The phosphoric acid groups provide strong complexing ability for calcium ions and enhance dispersibility; the quaternary ammonium salt groups improve the compatibility with clay minerals and significantly improve mud resistance; the two are combined with the flexible side chains of the long chain of the polyether macromonomer (TPEG) to form a multifunctional synergistic effect to meet the needs of complex environments.

[0057] The maleic rosin used in this patent is derived from natural resources and is renewable; when combined with other functional monomers, it not only enhances performance, but also reduces the proportion of traditional petrochemical-based materials used, achieving low-carbon and environmentally friendly goals. DETAILED DESCRIPTION

[0058] In order to better illustrate the purpose, technical solutions and advantages of the present invention, the present invention will be further described below in conjunction with specific embodiments.

[0059] In the examples, the test methods used are conventional methods unless otherwise specified, and the materials, reagents, etc. used are all commercially available unless otherwise specified.

[0060] Example 1

[0061] 1. Preparation of anti-mud monomer

[0062] In a three-necked flask, add methacryloyloxyethyl phosphate HMPA (20 g), acrylamidopropyl trimethyl ammonium chloride APTAC (40 g, 50 wt % aqueous solution) and 40 g of deionized water, stir evenly to obtain a mixed solution;

[0063] The mixed solution was heated to 70°C and stirred continuously at a constant temperature. A mixed solution of potassium persulfate (0.2 g), sodium bisulfite (0.1 g) and 10 g of deionized water was added dropwise to the mixed solution for 1 hour. After the addition was completed, the temperature was maintained at 70°C for 2 hours to obtain an anti-mud monomer.

[0064] 2. Preparation of air-entraining monomer

[0065] S110, adding 50 g of maleic rosin and 100 mL of anhydrous dichloromethane into a dry three-necked flask, stirring to dissolve, and then cooling to 0° C. to obtain a maleic rosin solution;

[0066] S120, slowly drop a mixture of 25 g of acryloyl chloride and 20 mL of triethylamine into the maleic rosin solution under ice bath conditions (0° C.) for about 1 hour. After the dropwise addition is complete, the mixture is heated to room temperature and stirred for reaction for 4 hours. After the reaction is complete, the mixture is washed with deionized water for 3 times, the organic phase is separated and dried with anhydrous sodium sulfate, and the solvent is removed by rotary evaporation to obtain an air-entraining monomer.

[0067] 3. Preparation of anti-mud water reducing agent

[0068] S210, accurately weigh 180 g of ethylene glycol monovinyl ether with a molecular weight of 3000, 4 g of acrylic acid, 1 g of hydrogen peroxide, and 4 g of an air-entraining monomer, put them into a four-necked reaction flask, start stirring, add 150 g of deionized water, and stir the mixture solution to obtain a mother liquor;

[0069] S220, at room temperature, liquid A and liquid B are added dropwise at the same time, and the addition time of liquid A and liquid B is 60 minutes. After the addition is completed, the temperature is kept for 30 minutes, and 4g of 30wt.% sodium hydroxide solution is added to adjust the pH to 7-8 to obtain the anti-mud water reducing agent.

[0070] Among them, liquid A: 10g acrylic acid + 4g anti-mud monomer + 15g deionized water;

[0071] Solution B: 0.5g sodium hypophosphite + 1.5g thioglycolic acid + 30g deionized water.

[0072] Embodiment 2:

[0073] 1. Preparation of anti-mud monomer

[0074] In a three-necked flask, add methacryloyloxyethyl phosphate HMPA (20 g), acryloyloxyethyl trimethylammonium chloride (40 g, 50 wt % aqueous solution) and 40 g of deionized water, and stir evenly to obtain a mixed solution;

[0075] The mixed solution was heated to 70°C and stirred continuously at a constant temperature. A mixed solution of potassium persulfate (0.2 g) and sodium bisulfite (0.1 g) and 10 g of deionized water was added dropwise for 1 hour. After the addition was completed, the temperature was maintained at 70°C for 2 hours to obtain an anti-mud monomer.

[0076] 2. Preparation of air-entraining monomer

[0077] S110, adding 50 g of maleic rosin and 100 mL of anhydrous dichloromethane into a dry three-necked flask, stirring to dissolve, and then cooling to 5° C. to obtain a maleic rosin solution;

[0078] S120, slowly drop a mixture of 25 g of acryloyl chloride and 20 mL of triethylamine into the maleic rosin solution under ice bath conditions (5° C.) for about 1 hour. After the dropwise addition is complete, the mixture is heated to room temperature and stirred for reaction for 4 hours. After the reaction is complete, the mixture is washed with deionized water for 3 times, the organic phase is separated and dried with anhydrous sodium sulfate, and the solvent is removed by rotary evaporation to obtain an air-entraining monomer.

[0079] 3. Preparation of anti-mud water reducing agent

[0080] S210, accurately weigh 180 g of butanediol monovinyl polyethylene glycol ether with a molecular weight of 3000, 4 g of acrylic acid, 1 g of hydrogen peroxide, and 4 g of an air-entraining monomer, put them into a four-necked reaction flask, start stirring, add 150 g of deionized water, and stir the mixture solution to obtain a mother liquor;

[0081] S220, at room temperature, liquid A and liquid B are added dropwise at the same time, and the addition time of liquid A and liquid B is 60 minutes. After the addition is completed, the temperature is kept for 30 minutes, and 4g of 30wt.% sodium hydroxide solution is added to adjust the pH to 7-8 to obtain the anti-mud water reducing agent.

[0082] Among them, liquid A: 10g acrylic acid + 4g anti-mud monomer + 15g deionized water;

[0083] Solution B: 0.5g vitamin C + 1.5g thioglycolic acid + 30g deionized water.

[0084] Embodiment 3:

[0085] 1. Preparation of anti-mud monomer

[0086] In a three-necked flask, add methacryloyloxyethyl phosphate HMPA (20 g), methacryloyloxyethyl trimethylammonium chloride (40 g, 50 wt % aqueous solution) and 40 g of deionized water, stir evenly to obtain a mixed solution;

[0087] The mixed solution was heated to 70°C and stirred continuously at a constant temperature. A mixed solution of potassium persulfate (0.2 g) and sodium bisulfite (0.1 g) and 10 g of deionized water was added dropwise for 1 hour. After the addition was completed, the temperature was maintained at 70°C for 2 hours to obtain an anti-mud monomer.

[0088] 2. Preparation of air-entraining monomer

[0089] S110, add 50 g of maleic rosin and 100 mL of anhydrous dichloromethane into a dry three-necked flask, stir to dissolve, and then cool to 2° C. to obtain a maleic rosin solution;

[0090] S120, under ice bath conditions (2°C), slowly drop a mixed solution containing 25g of acryloyl chloride and 20mL of triethylamine into the maleic rosin solution for about 1 hour. After the dropwise addition is completed, the temperature is raised to room temperature and stirred for reaction for 4 hours. After the reaction is completed, the mixed solution is washed with deionized water for 3 times, the organic phase is separated and dried with anhydrous sodium sulfate, and the solvent is removed by rotary evaporation to obtain an air-entraining monomer.

[0091] 3. Preparation of anti-mud water reducing agent

[0092] S210, accurately weigh 180 g of 4-hydroxybutyl vinyl ether with a molecular weight of 3000, 4 g of acrylic acid, 1 g of hydrogen peroxide, and 4 g of an air-entraining monomer, put them into a four-necked reaction flask, start stirring, add 150 g of deionized water, and stir the mixture solution to obtain a mother liquor;

[0093] S220, at room temperature, liquid A and liquid B are added dropwise simultaneously for 60 minutes. After the addition is completed, the mixture is kept warm for 30 minutes, and 4 g of 30% sodium hydroxide solution is added to adjust the pH to obtain the anti-mud type water reducing agent.

[0094] Among them, liquid A: 10g acrylic acid + 4g anti-mud monomer + 15g deionized water;

[0095] Solution B: 0.5g vitamin C + 1.5g thioglycolic acid + 30g deionized water.

[0096] Comparative Example 1

[0097] The other steps are the same as those in Example 1, except that no anti-mud monomer is contained in the preparation of the water reducer, and the amount of water is adjusted so that the solid content of the water reducer prepared in Comparative Example 1 is the same as that in Example 1.

[0098] Comparative Example 1

[0099] The other steps are the same as those in Example 1, except that the air entraining monomer is not removed during the preparation of the water reducer, and the amount of water is adjusted so that the solid content of the water reducer prepared in Comparative Example 2 is the same as that in Example 1.

[0100] Comparative Example 3:

[0101] The commercially available common polycarboxylate water reducer Point-S has the same solid content as that of the embodiment and the comparative example.

[0102] Minfu P.042.5 cement was used to test the slump of concrete. The mix ratio of the experimental concrete was designed according to JGJ55 “Code for Design of Ordinary Concrete Mix Ratio”. The concrete mix ratio is shown in Table 1.

[0103] The concrete performance test refers to GB / T50080-2016 "Test method for performance of ordinary concrete mixtures" and GB / T50081-2016 "Test method for mechanical properties of ordinary concrete". The test data are shown in Table 2.

[0104] Table 1 Concrete mix ratio / m 3

[0105]

[0106] Table 2 Performance test results

[0107]

[0108] It can be seen from Table 2 that under the conditions of equal solid content of water reducer and without montmorillonite, the dispersion performance of Examples 1, 2 and 3 is better than that of Comparative Example 3, indicating that the synthesized branched structure anti-mud high-dispersion water reducer has considerable dispersion performance; when the montmorillonite content is increased to 5%, the dispersion performance of the commercially available water reducer is significantly reduced, while the dispersion performance of the anti-mud water reducer provided by the present invention is not much reduced compared with that without montmorillonite, indicating that the branched structure anti-mud high-dispersion water reducer described in the present invention has good dispersion retention and anti-mud performance, which is significantly better than the commercially available water reducer.

[0109] It should be noted that the specific parameters or some reagents in the above embodiments are specific embodiments or preferred embodiments of the present invention, rather than limiting the present invention; those skilled in the art can make adaptive adjustments within the scope of the present invention.

Claims

1. An anti-mud monomer, characterized in that: In parts by weight, the anti-mud monomer comprises:

2. The anti-mud monomer according to claim 1, characterized in that: The unsaturated phosphoric acid includes methacryloyloxyethyl phosphoric acid.

3. The anti-mud monomer according to claim 1, characterized in that: The unsaturated quaternary ammonium salt monomer includes at least one of acrylamidopropyl trimethyl ammonium chloride, methacryloyloxyethyl trimethyl ammonium chloride, acryloyloxyethyl trimethyl ammonium chloride and methacryloyloxypropyl trimethyl ammonium chloride.

4. The anti-mud monomer according to claim 1, characterized in that: The first oxidant includes at least one of potassium persulfate, hydrogen peroxide and ammonium persulfate.

5. The anti-mud monomer according to claim 1, characterized in that: The first reducing agent includes at least one of sodium bisulfite, sodium hypophosphite, sodium thiosulfate and vitamin C.

6. A method for preparing the anti-mud monomer according to any one of claims 1 to 5, characterized in that: Includes steps: Mixing unsaturated phosphoric acid, unsaturated quaternary ammonium salt monomer and water to obtain a mixed solution; The oxidizing agent aqueous solution and the reducing agent aqueous solution are added dropwise to the mixed solution, and after the addition is completed, the mixture is kept warm for reaction to obtain the anti-mud monomer.

7. An anti-mud water reducing agent, characterized in that: The invention comprises the anti-mud monomer according to any one of claims 1 to 5.

8. The anti-mud water reducing agent according to claim 7, characterized in that: In parts by weight, the raw materials for preparing the anti-mud and water-reducing agent include:

9. The anti-mud water reducing agent according to claim 8, characterized in that: In parts by weight, the raw materials for preparing the air entraining monomer include: 30-80 parts of Malay rosin; 20-30 parts of acylating agent; and 20-30 parts of catalyst.

10. A method for preparing an anti-mud water reducing agent according to any one of claims 7 to 9, characterized in that: Includes steps: mixing an air entraining monomer, an unsaturated polyether, an unsaturated acid, a second oxidant and water to obtain a mother solution; Add liquid A and liquid B dropwise to the mother liquor, continue to keep warm for 0.5 to 1.5 hours after the addition is completed, and adjust the pH value of the solution to 7 to 8 after the reaction is completed to obtain the anti-mud water reducing agent; Liquid A is a mixture of unsaturated acid, anti-mud monomer and water. The mass ratio of the unsaturated acid in liquid A to the unsaturated acid in the mother liquor is (10-15):15; Liquid B is an aqueous solution of a second reducing agent and a chain transfer agent.

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