Anti-mud monomer and preparation method thereof, anti-mud water reducing agent and preparation method thereof

Abstract

The present application relates to a kind of anti-mud monomer and its preparation method, anti-mud water reducing agent and its preparation method.The anti-mud monomer includes, by weight parts:20-30 parts of unsaturated phosphoric acid;30-50 parts of unsaturated quaternary ammonium salt monomer;0.1-0.4 parts of first oxidizing agent;0.1-0.4 parts of first reducing agent;And water.The water reducing agent provided in the present application contains phosphoric acid group, quaternary ammonium salt group, the strong complexing ability of phosphoric acid group is provided to calcium ion, and dispersibility is enhanced;Quaternary ammonium salt group improves the compatibility with clay mineral, and significantly improves the anti-mud property;The flexible side chain of long chain of both and polyether macromonomer (TPEG) is combined, forms multifunctional synergistic effect, meets the demand of complex environment.

Description

Technical Field

[0001] The present 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 superplasticizers (PCSs) have become a key component of concrete admixtures due to their excellent water-reducing properties and environmental friendliness, and are widely used in various projects. However, when high-clay mineral components such as bentonite and laterite are added to concrete raw materials, the performance of traditional PCSs is often significantly affected. This is primarily due to the large specific surface area and strong adsorption properties of layered silicates (such as montmorillonite) contained in high-clay minerals, which tend to over-adsorb the active molecules of the PCSs, thereby weakening its dispersion on the cement particle surface. This phenomenon often leads to problems such as slump loss and deterioration of workability, seriously affecting the concrete's construction performance and project quality. 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, in parts by weight:

[0006]

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

[0008] In some embodiments, the unsaturated quaternary ammonium salt monomer includes at least one of acrylamidopropyltrimethylammonium chloride, methacryloyloxyethyltrimethylammonium chloride, acryloyloxyethyltrimethylammonium chloride and methacryloyloxypropyltrimethylammonium chloride.

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

[0010] In some embodiments, the first oxidizing agent 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 amount of water is 30-60 parts by mass.

[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] An oxidizing agent aqueous solution and a reducing agent aqueous solution are added dropwise to the mixed solution, and the mixture is kept warm for reaction after the addition is completed, thereby obtaining an anti-mud monomer.

[0017] In some embodiments, an aqueous oxidizing agent solution and an aqueous reducing agent solution are added dropwise to the mixed solution at the same time.

[0018] In some embodiments, the oxidant aqueous solution is added dropwise for 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, in parts 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, dropwise adding a mixed solution of a catalyst and an acylating agent into the maleic rosin solution, stirring and reacting after the dropwise addition is completed, and the air-entraining monomer is obtained 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 hour to 3 hours, preferably 1 hour.

[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 hours to 6 hours, preferably 4 hours.

[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 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 solution A and solution B dropwise to the mother liquor, continuing the heat-insulating 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 to obtain the anti-mud 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, based on 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 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 with reference to 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, 20 g of methacryloyloxyethyl phosphate HMPA, 40 g of acrylamidopropyltrimethylammonium chloride APTAC (50 wt% aqueous solution) and 40 g of deionized water were added and stirred 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 (0.2g), sodium bisulfite (0.1g) and 10g 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 to a dry three-necked flask, stirring to dissolve, and then cooling to 0° C. to obtain a maleic rosin solution;

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

[0067] 3. Preparation of anti-mud water reducer

[0068] S210, accurately weighing 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, placing the mixture into a four-necked reaction flask, starting stirring, adding 150 g of deionized water, and stirring the mixture to obtain a mother liquor;

[0069] 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 wt.% 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] Example 2:

[0073] I. Preparation of anti-mud monomer

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

[0075] Heat the mixed solution to 70°C, and continue to stir at constant temperature. Add a mixed solution of potassium persulfate (0.2 g) and sodium bisulfite (0.1 g) in 10 g of deionized water dropwise, with a dropwise time of 1 hour. After the dropwise addition is complete, maintain the temperature at 70°C for 2 hours to obtain the anti-mud monomer.

[0076] II. Preparation of air entraining monomer

[0077] S110, add 50 g of maleic rosin and 100 mL of anhydrous dichloromethane to a dry three-necked flask, stir to dissolve, and then cool to 5°C to obtain a maleic rosin solution;

[0078] S120, under ice bath conditions (5°C), slowly add a mixed solution containing 25 g of acryloyl chloride and 20 mL of triethylamine to the maleic rosin solution, with a dropwise time of about 1 hour. After the dropwise addition is complete, warm to room temperature and stir for 4 hours. After the reaction is complete, wash the mixed solution with deionized water 3 times, separate the organic phase and dry with anhydrous sodium sulfate, and remove the solvent by rotary evaporation to obtain the air entraining monomer.

[0079] III. Preparation of anti-mud type 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 air entraining monomer, and place them in a four-necked reaction flask. Start stirring, add 150 g of deionized water, and stir the mixed solution until uniform to obtain a mother liquor;

[0081] S220, simultaneously add A liquid and B liquid at room temperature, with a dropwise time of 60 min for each. After the dropwise addition is complete, maintain the temperature for 30 min, and then add 4 g of 30 wt.% sodium hydroxide solution to adjust the pH to 7-8 to obtain the anti-mud type water reducing agent.

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

[0083] B liquid: 0.5 g of vitamin C + 1.5 g of mercaptoacetic acid + 30 g of deionized water.

[0084] Example 3:

[0085] I. Preparation of anti-mud monomer

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

[0087] Heat the mixed solution to 70°C, and continue to stir at constant temperature. Add a mixed solution of potassium persulfate (0.2 g) and sodium bisulfite (0.1 g) and 10 g of deionized water dropwise, and the dropwise time is 1 hour. After the dropwise addition is completed, keep the temperature at 70°C for 2 hours to obtain the anti-mud monomer.

[0088] II. Preparation of air entraining monomer

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

[0090] S120, slowly add a mixed solution containing 25 g of acryloyl chloride and 20 mL of triethylamine to the maleic rosin solution under ice bath conditions (2°C), and the dropwise time is about 1 hour. After the dropwise addition is completed, warm up to room temperature and stir for 4 hours. After the reaction is completed, wash the mixture with deionized water 3 times, separate the organic phase and dry it with anhydrous sodium sulfate, and remove the solvent by rotary evaporation to obtain the air entraining monomer.

[0091] III. Preparation of anti-mud type 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 air entraining monomer, and place them into a four-necked reaction flask. Start stirring, add 150 g of deionized water, stir the mixture solution uniformly to obtain a mother liquor;

[0093] S220, add A and B liquids simultaneously at room temperature, and the dropwise time is 60 min. After the dropwise addition is completed, keep warm for 30 min, and add 4 g of 30% sodium hydroxide solution to adjust the pH to obtain the anti-mud type water reducing agent.

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

[0095] B liquid: 0.5 g of vitamin C + 1.5 g of mercaptoacetic acid + 30 g of deionized water.

[0096] Comparative Example 1

[0097] The other steps are the same as those of Example 1, except that the anti-mud monomer is not contained in the preparation of the water reducing agent, and the amount of water is adjusted so that the solid content of the water reducing agent prepared in Comparative Example 1 is the same as that of Example 1.

[0098] Comparative Example 1

[0099] Other steps are the same as Example 1, except that the air entraining monomer is removed in the preparation of the water reducing agent, and the amount of water is adjusted so that the solid content of the water reducing agent prepared in Comparative Example 2 is the same as that of Example 1.

[0100] Comparative Example 3:

[0101] The commercially available ordinary polycarboxylic acid water reducing agent Point-S has the same solid content as the examples and comparative examples.

[0102] The slump of the concrete is tested using Minfu P.042.5 cement, and the concrete mix design is referred to JGJ55 “Code for Design of Concrete Mix Proportion”. The concrete mix is shown in Table 1.

[0103] The concrete performance test is referred to GB / T50080-2016 “Test Methods for Performance of Ordinary Concrete Mixture” and GB / T50081-2016 “Test Methods for Mechanical Properties of Ordinary Concrete”. The test data is shown in Table 2.

[0104] Table 1 Concrete Mix Proportion / m 3

[0105]

[0106] Table 2 Performance Test Results

[0107]

[0108] As shown in Table 2, under the condition of the same solid content of the water reducing agent and without adding montmorillonite, the dispersion performance of Examples 1, 2 and 3 is better than that of Comparative Example 3, which shows that the branched structure anti-mud high dispersion water reducing agent has good dispersion performance. When the montmorillonite content is increased to 5%, the dispersion performance of the commercially available water reducing agent is significantly reduced, while the dispersion performance of the anti-mud water reducing agent provided by the present application is not greatly reduced, which shows that the branched structure anti-mud high dispersion water reducing agent has good dispersion retention and anti-mud performance, and is significantly better than the commercially available water reducing agent.

[0109] It should be noted that the specific parameters or some reagents in the above examples are specific embodiments or preferred embodiments under the concept of the present application, but not a limitation; those skilled in the art can make adaptive adjustments within the concept and protection scope of the present application.

Claims

1. An anti-mud water reducing agent, characterized in that: In parts by weight, the raw materials for preparing the anti-mud water-reducing agent include: 3-6 parts of anti-mud monomer; 3-6 parts of air entraining monomer; 180-200 parts of unsaturated polyether; 13-18 parts of unsaturated acid; 1-2 parts of the second oxidant; 0.1-1.1 parts of the second reducing agent; 1-2 parts of chain transfer agent; and water; The raw materials for preparing the air entraining monomer include, in parts by weight: 30-80 parts of Malay rosin; 20-30 parts of an acylating agent; and 20-30 parts of catalyst; The anti-mud monomer includes: 20-30 parts of unsaturated phosphoric acid; 30-50 parts of unsaturated quaternary ammonium salt monomer; 0.1-0.4 parts of the first oxidizing agent; 0.1-0.4 parts of a first reducing agent; and water; The unsaturated phosphoric acid is methacryloyloxyethyl phosphoric acid; The catalyst is at least one of triethylamine, diisopropylethylamine and sodium carbonate; The acylating agent is at least one of methacryloyl chloride and acryloyl chloride.

2. The anti-mud water reducing agent according to claim 1, characterized in that: The unsaturated polyether includes at least one of ethylene glycol monovinyl ether, 4-hydroxybutyl vinyl ether and butanediol monovinyl polyethylene glycol ether.

3. The anti-mud water reducing agent according to claim 1, characterized in that: The unsaturated acid includes at least one of acrylic acid and methacrylic acid.

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

5. The anti-mud water reducing agent according to claim 1, characterized in that: The second reducing agent includes at least one of sodium sulfite, sodium hypophosphite and sodium thiosulfate.

6. The anti-mud water reducing agent according to claim 1, characterized in that: The chain transfer agent includes thioglycolic acid, sodium bisulfite, mercaptoethanol or mercaptopropionic acid.

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

8. The anti-mud water reducing agent 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.

9. A method for preparing the anti-mud water reducing agent according to any one of claims 1 to 8, characterized in that: Including steps: mixing an air-entraining monomer, an unsaturated polyether, an unsaturated acid, a second oxidant and water to obtain a mother liquor; Add solution A and solution B dropwise to the mother liquor, continue to keep warm and react 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 reducer; Liquid A is a mixture of unsaturated acid, anti-mud monomer and water. The mass ratio of unsaturated acid in liquid A to unsaturated acid in 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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