Maleic rosin modified polyether macro-monomer, preparation method thereof, water reducing agent and preparation method thereof

Abstract

The present application relates to a kind of rosin modified polyether macromonomer and its preparation method, water reducing agent and its preparation method, a kind of rosin modified polyether macromonomer, preparation raw material of the rosin modified polyether macromonomer includes: ethylene glycol monovinyl polyethylene glycol ether 40~50 parts;Modified rosin 10~20 parts;Wherein, preparation raw material of the modified rosin includes: rosin 10~20 parts;Epichlorohydrin 5~10 parts;Catalyst 0.1~0.5 parts by weight fraction.The rosin modified polyether macromonomer of the present application is modified by rosin, the hydrophobic cyclic structure and long chain in the structure of rosin are introduced into rosin modified polyether macromonomer, when it is applied to water reducing agent, make water reducing agent have excellent air entraining ability, and bubble stability is higher, while ensuring that water reducing agent molecular structure has high efficiency dispersibility and stability, meet the needs of different cement systems.

Description

Technical Field

[0001] This invention relates to the field of concrete admixture technology, specifically to a maleic rosin-modified polyether macromonomer and its preparation method, and a water-reducing agent and its preparation method. Background Technology

[0002] Polycarboxylate superplasticizers, as the third generation of high-efficiency water-reducing agents, have been widely used in modern concrete engineering due to their low dosage, high water reduction rate, strong environmental friendliness, and excellent dispersibility. Compared with traditional naphthalene-based and aliphatic water-reducing agents, polycarboxylate superplasticizers have significant advantages in terms of the designability of their molecular structure. By controlling the functional groups of their main chain and side chains, the performance of the water-reducing agent can be significantly improved, and its adaptability to different cement systems can be enhanced.

[0003] In modern concrete technology, air-entraining agents, by introducing tiny and stable air bubbles, can significantly improve the frost resistance, impermeability, and durability of concrete. However, traditional air-entraining agents have poor compatibility with water-reducing agents, often leading to instability in concrete performance and limiting their application effectiveness. Although polycarboxylate superplasticizers have excellent dispersibility and environmental characteristics, their ability to control microbubbles in concrete remains limited. Summary of the Invention

[0004] Therefore, it is necessary to provide a maleic rosin-modified polyether macromonomer with the ability to regulate air bubbles in concrete, its preparation method, and a water-reducing agent and its preparation method.

[0005] To achieve the above objectives, the present invention provides a technical solution:

[0006] A maleic rosin-modified polyether macromonomer, wherein the raw materials for preparing the maleic rosin-modified polyether macromonomer, by weight parts, include:

[0007] 40-50 parts of unsaturated polyether;

[0008] 10-20 parts of modified Malaysian rosin;

[0009] The raw materials for preparing the modified maleic rosin, by weight, include:

[0010] 10-20 parts of Malaysian rosin;

[0011] 5 to 10 parts of epichlorohydrin and / or propylene oxide;

[0012] Catalyst 0.1 to 0.5 parts.

[0013] In some embodiments, the unsaturated polyether includes at least one of ethylene glycol monovinyl polyethylene glycol ether, 4-hydroxybutyl vinyl ether, diethylene glycol monovinyl ether, diethylene glycol monoallyl ether, and triethylene glycol divinyl ether, preferably ethylene glycol monovinyl polyethylene glycol ether.

[0014] In some embodiments, the catalyst comprises p-toluenesulfonic acid.

[0015] In some embodiments, the molecular weight of ethylene glycol monovinyl polyethylene glycol ether is 2400 to 2800, preferably 2400.

[0016] This invention also provides a method for preparing maleic rosin-modified polyether macromonomers, comprising the following steps:

[0017] Modified maleic rosin was added dropwise to molten ethylene glycol monovinyl polyethylene glycol ether and reacted. After the reaction was completed, maleic rosin-modified polyether macromonomer was obtained.

[0018] In some embodiments, the temperature of the molten ethylene glycol monovinyl polyethylene glycol ether is 80–90°C, preferably 80°C.

[0019] In some embodiments, the reaction temperature for obtaining the maleic rosin-modified polyether macromonomer is 80°C to 100°C.

[0020] In some embodiments, the reaction time to obtain the maleic rosin-modified polyether macromonomer is 2h to 3h.

[0021] In some embodiments, the preparation steps of the modified maleic rosin include:

[0022] S110. Dissolve maleic rosin in a solvent to obtain a maleic rosin solution;

[0023] S120. Add a catalyst to the rosin solution and stir to dissolve to obtain a mixture;

[0024] S130. Epichlorohydrin is added dropwise to the mixture for reaction. After the reaction is complete, modified maleic rosin is obtained.

[0025] In some embodiments, the reaction time for adding epichlorohydrin to the mixture in step S130 is 2 to 3 hours.

[0026] In some embodiments, during the epichlorohydrin reaction in step S130, the reaction temperature is 60°C to 80°C.

[0027] In some embodiments, in step S130, the obtained modified maleic rosin is washed with a washing solvent to remove unreacted substances and byproducts.

[0028] In some embodiments, the washing solvent includes anhydrous ethanol.

[0029] In some embodiments, the solvent includes at least one of toluene, anhydrous ethanol, xylene, and dichloromethane.

[0030] This invention provides a water-reducing agent, the raw material of which is a maleic rosin-modified polyether macromonomer. The raw materials for preparing the water-reducing agent include:

[0031]

[0032] In some embodiments, the unsaturated acid includes at least one of acrylic acid and methacrylic acid, preferably acrylic acid.

[0033] In some embodiments, the oxidant includes at least one of hydrogen peroxide, ammonium persulfate, and potassium persulfate, preferably hydrogen peroxide.

[0034] In some embodiments, the reducing agent includes at least one of sodium sulfite, sodium hypophosphite, and sodium thiosulfate, preferably sodium hypophosphite.

[0035] In some embodiments, the chain transfer agent includes mercaptoacetic acid, sodium bisulfite, mercaptoethanol, mercaptopropionic acid, preferably mercaptoacetic acid.

[0036] This invention provides a method for preparing a water-reducing agent, comprising the following steps:

[0037] S210. Mix maleic rosin-modified polyether macromonomer, unsaturated acid, oxidant and water to obtain mother liquor;

[0038] S220. Add solution A and solution B dropwise to the mother liquor. After the addition is complete, continue to keep the reaction at a warm temperature for 0.5 to 1.5 hours. After the reaction is complete, adjust the pH of the solution to 7 to 8 to obtain the water-reducing agent.

[0039] Among them, solution A is a mixture of unsaturated acid and water, and the mass ratio of unsaturated acid in solution A to unsaturated acid in the mother liquor is (10-15):15.

[0040] Solution B is an aqueous solution of a reducing agent and a chain transfer agent.

[0041] In some embodiments, in step S220, the dripping time of liquid A is 1 to 3 hours, and the dripping time of liquid B is 1 to 3 hours.

[0042] In some embodiments, in step S220, 2 to 5 parts by weight of alkali solution are added to adjust the pH value to 7 to 8.

[0043] In some of these embodiments, the alkali solution comprises 30 wt.% sodium hydroxide.

[0044] The beneficial effects of this invention are:

[0045] The modified polyether macromonomer of maleic rosin of the present invention modifies maleic rosin by introducing the hydrophobic ring structure and long chain in the maleic rosin structure into the modified polyether macromonomer. When applied to water-reducing agents, it gives the water-reducing agents excellent air-entraining ability and high bubble stability, while ensuring the efficient dispersibility and stability of the water-reducing agent molecular structure, thus meeting the needs of different cement systems.

[0046] This patent, by introducing the unique hydrophobic and macrocyclic structure of Malaysian rosin, not only optimizes the air-entraining capacity of concrete paste but also enhances the uniformity and stability of air bubbles through molecular design. This modified PCE can significantly improve the freeze-thaw resistance and impermeability of concrete while maintaining good water reduction rate and workability.

[0047] This patent innovatively uses biomass as a synthetic raw material, which can effectively reduce carbon emissions and promote the transformation of the concrete industry towards a green and low-carbon direction. Detailed Implementation

[0048] To better illustrate the purpose, technical solution, and advantages of the present invention, the present invention will be further described below in conjunction with specific embodiments.

[0049] In the embodiments, unless otherwise specified, the experimental methods used are conventional methods, and the materials and reagents used are commercially available unless otherwise specified.

[0050] Example 1

[0051] I. Preparation of Modified Maleic Rosin

[0052] S110. Dissolve 10g of maleic rosin in 50mL of toluene and stir evenly at 60℃ to obtain a maleic rosin solution.

[0053] S120. Add 0.2g of p-toluenesulfonic acid to the rosin solution and stir continuously until completely dissolved to obtain a mixture.

[0054] S130. Slowly add 6g of epichlorohydrin over 30 minutes, maintain the reaction temperature, and continue stirring for 2 hours to produce modified maleic rosin.

[0055] II. Preparation of Maleic Rosin-Modified Polyether Macromonomers

[0056] 40g of ethylene glycol monovinyl polyethylene glycol ether (molecular weight 2400) was heated to a molten state (approximately 80°C), and then 10g of modified maleic rosin was slowly added dropwise. The reaction temperature was maintained at 80°C–100°C for 2 hours. After the reaction was complete, the mixture was cooled to room temperature, and 100mL of anhydrous ethanol was added to wash the reaction product to remove unreacted substances and byproducts, yielding the maleic rosin-modified polyether macromonomer.

[0057] III. Preparation of Water-Reducing Agent

[0058] S210. Accurately weigh 180g of maleic rosin-modified polyether macromonomer, 4g of acrylic acid, and 1g of hydrogen peroxide, put them into a four-necked reaction flask, turn on the stirrer, add 150g of deionized water, and stir the mixture solution evenly to obtain the mother liquor.

[0059] S220. At room temperature, solution A and solution B are added dropwise to the mother liquor simultaneously. Solution A is added dropwise for 1 hour, and solution B is added dropwise for 1 hour. After the addition is completed, the reaction is kept at the temperature for 0.5 hours. Then, 4g of 30wt.% sodium hydroxide solution is added to adjust the pH to 7-8 to obtain the water-reducing agent.

[0060] Solution A consists of 14g acrylic acid and 15g deionized water.

[0061] Solution B: Sodium hypophosphite 0.5g + mercaptoacetic acid 1.5g + deionized water 30g.

[0062] Example 2

[0063] I. Preparation of Modified Maleic Rosin

[0064] S110. Dissolve 10g of maleic rosin in 50mL of dichloromethane and stir until homogeneous at 80℃ to obtain a maleic rosin solution.

[0065] S120. Add 0.2g of p-toluenesulfonic acid to the rosin solution and stir continuously until completely dissolved to obtain a mixture.

[0066] S130. Slowly add 6g of epichlorohydrin over 30 minutes, maintain the reaction temperature, and continue stirring for 2 hours to produce modified maleic rosin.

[0067] II. Preparation of Maleic Rosin-Modified Polyether Macromonomers

[0068] 40g of ethylene glycol monovinyl polyethylene glycol ether (molecular weight 2400) was heated to a molten state (approximately 80°C), and then 15g of modified maleic rosin was slowly added dropwise. The reaction temperature was maintained at 80°C–100°C for 2 hours. After the reaction was complete, the mixture was cooled to room temperature, and 100mL of anhydrous ethanol was added to wash the reaction product to remove unreacted substances and byproducts, yielding the maleic rosin-modified polyether macromonomer.

[0069] III. Preparation of Water-Reducing Agent

[0070] S210. Accurately weigh 180g of maleic rosin-modified polyether macromonomer, 4g of acrylic acid, and 1g of hydrogen peroxide, put them into a four-necked reaction flask, turn on the stirrer, add 150g of deionized water, and stir the mixture solution evenly to obtain the mother liquor.

[0071] S220, solutions A and B are added dropwise simultaneously at room temperature. Solution A is added dropwise for 1 hour, and solution B is added dropwise for 1 hour. After the addition is completed, the solution is kept warm for 30 minutes, and 4g of 30wt.% sodium hydroxide solution is added to adjust the pH to obtain the water-reducing agent.

[0072] Solution A consists of 14g acrylic acid and 15g deionized water.

[0073] Solution B: Sodium hypophosphite 0.5g + mercaptoacetic acid 1.5g + deionized water 30g.

[0074] Example 3

[0075] I. Preparation of Modified Maleic Rosin

[0076] S110. Dissolve 10g of maleic rosin in 50mL of anhydrous toluene and stir until homogeneous at 70℃ to obtain a maleic rosin solution.

[0077] S120. Add 0.2g of p-toluenesulfonic acid to the rosin solution and stir continuously until completely dissolved to obtain a mixture.

[0078] S130. Slowly add 6g of epichlorohydrin over 30 minutes, maintain the reaction temperature, and continue stirring for 2 hours to produce modified maleic rosin.

[0079] II. Preparation of Maleic Rosin-Modified Polyether Macromonomers

[0080] 40g of ethylene glycol monovinyl polyethylene glycol ether (molecular weight 2400) was heated to a molten state (approximately 80°C), and then 10g of modified maleic rosin was slowly added dropwise. The reaction temperature was maintained at 80°C–100°C for 2 hours. After the reaction was complete, the mixture was cooled to room temperature, and 100mL of anhydrous ethanol was added to wash the reaction product to remove unreacted substances and byproducts, yielding the maleic rosin-modified polyether macromonomer.

[0081] III. Preparation of Water-Reducing Agent

[0082] S210. Accurately weigh 180g of maleic rosin-modified polyether macromonomer, 4g of 30wt.% sodium hydroxide solution, and 1g of hydrogen peroxide, put them into a four-necked reaction flask, turn on the stirrer, add 150g of deionized water, and stir the mixture solution evenly to obtain the mother liquor.

[0083] S220 solution and solutions A and B are added dropwise simultaneously at room temperature for 1 hour. After the addition is complete, the solution is kept at this temperature for 30 minutes, and then 4g of 30wt.% sodium hydroxide solution is added to adjust the pH to obtain the water-reducing agent.

[0084] Solution A consists of 18g acrylic acid + 15g deionized water.

[0085] Solution B: Sodium hypophosphite 0.5g + mercaptoacetic acid 1.5g + deionized water 30g.

[0086] Comparative Example 1

[0087] The other steps are the same as in Example 1, except that when preparing the maleic rosin-modified polyether macromonomer, ethylene glycol monovinyl polyethylene glycol ether (molecular weight 2400) is replaced by an equal amount of ethylene glycol monovinyl polyethylene glycol ether (molecular weight 3000), and the reaction time for preparing the maleic rosin-modified polyether macromonomer is 2 hours.

[0088] Comparative Example 2

[0089] The other steps are the same as in Example 1, except that when preparing the water-reducing agent, the maleic rosin-modified polyether macromonomer is replaced with isopentenyl polyoxyethylene ether, and the solid content of the resulting water-reducing agent is the same as in Example 1.

[0090] Comparative Example 3

[0091] The other steps are the same as in Example 1, except for the step of preparing modified maleic rosin. When preparing the modified maleic rosin polyether macromonomer, the modified maleic rosin is replaced with an equal amount of maleic rosin, and the solid content of the resulting water-reducing agent is the same as in Example 1.

[0092] Comparative Example 4

[0093] The commercially available air-entrained polycarboxylate superplasticizer PCE-YQ has the same solids content as the superplasticizer prepared in Example 1.

[0094] The slump of the concrete was tested using Minfu P.042.5 cement. The concrete mix design was based on JGJ55 "Specification for Mix Design of Ordinary Concrete", and the concrete mix proportions are shown in Table 1. The concrete performance was tested according to GB / T50080-2016 "Test Methods for Performance of Ordinary Concrete Mixtures", and the test data are shown in Table 2.

[0095] Table 1 Concrete mix proportions / m 3

[0096] Intensity level cement / kg Manufactured sand / kg Crushed stone (10-20mm) / kg Water / kg C30 360 840 1020 175

[0097] Table 2 Performance Test Results

[0098] sample Solid dosage / % Initial slump / mm Initial expansion / mm Initial gas content / % 7d compressive strength / MPa Example 1 0.2 220 530 4.8 31.3 Example 2 0.21 210 520 4.1 31.8 Example 3 0.22 210 525 4.4 32.3 Comparative Example 1 0.24 220 530 2.1 32 Comparative Example 2 0.24 200 500 2.0 31.9 Comparative Example 3 0.24 175 440 3.1 30.8 Comparative Example 4 0.24 210 535 2.3 31.9

[0099] As can be seen from Table 2, the product in the example has a high water reduction rate and excellent air entrainment performance. Moreover, while introducing air bubbles, it has little impact on the concrete strength. Its performance is significantly better than that of commercially available air-entraining water-reducing agents. This indicates that when using the maleic rosin-modified polyether macromonomer synthetic water-reducing agent mentioned in the invention, the air entrainment and dispersion performance of the water-reducing agent can be significantly improved.

[0100] It should be noted that the specific parameters or reagents in the above embodiments are specific or preferred embodiments under the concept of the present invention, and not limitations thereof; those skilled in the art can make adaptive adjustments within the concept and protection scope of the present invention.

Claims

1. A maleic rosin-modified polyether macromonomer, characterized in that, The raw materials for preparing the maleic rosin-modified polyether macromonomer, by weight, include: 40-50 parts of unsaturated polyether; 10-20 parts of modified Malaysian rosin; The raw materials for preparing the modified maleic rosin, by weight, include: 10-20 parts of Malaysian rosin; 5-10 parts of epichlorohydrin and / or propylene oxide; Catalyst 0.1~0.5 parts; The unsaturated polyether is ethylene glycol monovinyl polyethylene glycol ether with a molecular weight of 2400.

2. The maleic rosin-modified polyether macromonomer according to claim 1, characterized in that, The catalyst includes p-toluenesulfonic acid.

3. A method for preparing the maleic rosin-modified polyether macromonomer as described in any one of claims 1 to 2, characterized in that, Including the following steps: Modified maleic rosin was added dropwise to molten ethylene glycol monovinyl polyethylene glycol ether and reacted. After the reaction was completed, maleic rosin-modified polyether macromonomer was obtained.

4. The method for preparing the maleic rosin-modified polyether macromonomer according to claim 3, characterized in that, The preparation steps of the modified maleic rosin include: Dissolve maleic rosin in a solvent to obtain a maleic rosin solution; A catalyst was added to the rosin solution, and the mixture was stirred to dissolve it, thus obtaining a mixture. Epichlorohydrin was added dropwise to the mixture to react with the mixture. After the reaction was completed, modified maleic rosin was obtained.

5. The method for preparing the maleic rosin-modified polyether macromonomer according to claim 4, characterized in that, In the step of adding epichlorohydrin dropwise to the mixture, the reaction time is 2h~3h.

6. The method for preparing the maleic rosin-modified polyether macromonomer according to claim 4, characterized in that, In the reaction of adding epichlorohydrin dropwise to the mixture, the reaction temperature is 60℃~80℃.

7. The method for preparing the maleic rosin-modified polyether macromonomer according to claim 4, characterized in that, The solvent includes at least one of toluene, anhydrous ethanol, xylene, and dichloromethane.

8. A water-reducing agent, wherein the raw materials for its preparation comprise the maleic rosin-modified polyether macromonomer as described in any one of claims 1 to 2.

9. A method for preparing the water-reducing agent as described in claim 8, characterized in that, The raw materials for preparing the water-reducing agent include: 180-200 parts of Malaysian rosin-modified polyether macromonomer; 15-20 parts of unsaturated acid; 1-4 parts oxidant; 0.2~0.8 parts of reducing agent; Chain transfer agent 0.2~0.8 parts; and water.

10. A method for preparing the water-reducing agent as described in claim 8, characterized in that, Including the following steps: A mother liquor was obtained by mixing maleic rosin-modified polyether macromonomer, unsaturated acid, oxidant and water. Add solution A and solution B dropwise to the mother liquor. After the addition is complete, continue to keep the reaction at the temperature for 0.5 to 1.5 hours. After the reaction is complete, adjust the pH of the solution to 7 to 8 to obtain the water-reducing agent. Among them, solution A is a mixture of unsaturated acid and water, and the mass ratio of unsaturated acid in solution A to unsaturated acid in the mother liquor is (10~15):15; Solution B is an aqueous solution of a reducing agent and a chain transfer agent.

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