Maleic rosin modified polyether macromonomer and preparation method thereof, and water reducing agent and preparation method thereof

Abstract

The invention relates to a maleated rosin modified polyether macromonomer and a preparation method thereof, and a water reducing agent and a preparation method thereof, and the maleated rosin modified polyether macromonomer is prepared from the following raw materials in parts by weight: 40-50 parts of ethylene glycol monovinyl polyethylene glycol ether; 10 to 20 parts of modified maleated rosin; wherein the modified maleated rosin is prepared from the following raw materials in parts by weight: 10 to 20 parts of maleated rosin; 5 to 10 parts of epoxy chloropropane; and 0.1 to 0.5 part of a catalyst. According to the maleated rosin modified polyether macromonomer disclosed by the invention, the maleated rosin is modified, a hydrophobic ring structure and a long chain in a maleated rosin structure are introduced into the maleated rosin modified polyether macromonomer, and when the maleated rosin modified polyether macromonomer is applied to a water reducing agent, the water reducing agent has excellent air entraining capability and relatively high bubble stability; meanwhile, the efficient dispersity and stability of the molecular structure of the water reducer are ensured, and the requirements of different cement systems are met.

Description

Technical Field

[0001] The invention relates to the technical field of concrete admixtures, in particular to a maleated rosin-modified polyether macromonomer and a preparation method thereof, a water reducing agent and a preparation method thereof. Background Art

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

[0003] In modern concrete technology, air-entraining agents can significantly improve the frost resistance, impermeability and durability of concrete by introducing tiny and stable bubbles. However, the poor compatibility of traditional air-entraining agents with water-reducing agents often leads to instability in concrete performance, which restricts its application effect. Although polycarboxylate water-reducing agents have excellent dispersibility and environmental protection properties, their ability to regulate microbubbles in concrete is still limited. Summary of the invention

[0004] Based on this, it is necessary to provide a maleic rosin-modified polyether macromonomer and a preparation method thereof, a water reducer and a preparation method thereof that have the ability to regulate bubbles in concrete.

[0005] To achieve the above object, 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 include, in parts by weight:

[0007] 40-50 parts of unsaturated polyether;

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

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

[0010] 10-20 parts of Malay rosin;

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

[0012] Catalyst 0.1-0.5 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 includes p-toluenesulfonic acid.

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

[0016] The present invention also provides a method for preparing a maleated rosin modified polyether macromonomer, comprising the steps of:

[0017] The modified maleic rosin is added dropwise into molten ethylene glycol monovinyl polyethylene glycol ether for reaction, and after the reaction is completed, a maleic rosin modified polyether macromonomer is obtained.

[0018] In some embodiments, the temperature of the ethylene glycol monovinyl polyglycol ether in the molten state is 80-90°C, preferably 80°C.

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

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

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

[0022] S110, dissolving maleic rosin in a solvent to obtain a maleic rosin solution;

[0023] S120, adding a catalyst to the maleic rosin solution, stirring and dissolving to obtain a mixed solution;

[0024] S130, epichlorohydrin is added dropwise to the mixed solution for reaction, and after the reaction is completed, modified maleic rosin is obtained.

[0025] In some embodiments, in step S130, epichlorohydrin is added dropwise to the mixed solution for reaction, and the reaction time is 2 h to 3 h.

[0026] In some embodiments, in step S130, when epichlorohydrin is added dropwise to the mixed solution for reaction, the reaction temperature is 60° C. to 80° C.

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

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

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

[0030] The present invention provides a water reducer, wherein the raw material for preparing the water reducer is maleic rosin modified polyether macromonomer, and the raw materials for preparing the water reducer 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 thioglycolic acid, sodium bisulfite, mercaptoethanol, and mercaptopropionic acid, preferably thioglycolic acid.

[0036] The present invention provides a method for preparing a water reducing agent, comprising the steps of:

[0037] S210, mixing a maleic rosin modified polyether macromonomer, an unsaturated acid, an oxidant and water to obtain a mother solution;

[0038] S220, adding solution A and solution B dropwise to the mother solution, and continuing the reaction by heat preservation 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 water reducing agent;

[0039] Wherein, liquid A is a mixture of unsaturated acid 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;

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

[0041] 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.

[0042] 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.

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

[0044] Beneficial effects of the present invention:

[0045] The maleic rosin modified polyether macromonomer of the invention introduces the hydrophobic ring structure and the long chain in the maleic rosin structure into the maleic rosin modified polyether macromonomer by modifying the maleic rosin. When the maleic rosin modified polyether macromonomer is applied to a water reducer, the water reducer has excellent air entraining capacity and high bubble stability, and at the same time ensures the efficient dispersibility and stability of the molecular structure of the water reducer, thereby meeting the requirements of different cement systems.

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

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

[0048] 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.

[0049] 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.

[0050] Example 1

[0051] 1. Preparation of modified maleic rosin

[0052] S110, dissolving 10 g of maleic rosin in 50 mL of toluene, and stirring evenly at 60° C. to obtain a maleic rosin solution;

[0053] S120, adding 0.2 g of p-toluenesulfonic acid to the maleic rosin solution, and continuing to stir until it is completely dissolved to obtain a mixed solution;

[0054] S130, slowly drop 6 g of epichlorohydrin within 30 min, maintain the reaction temperature, and continue stirring the reaction for 2 hours to generate modified maleic rosin.

[0055] 2. Preparation of maleic rosin modified polyether macromonomer

[0056] 40g of ethylene glycol monovinyl polyglycol ether (molecular weight 2400) was heated to a molten state (about 80°C), and then 10g of modified maleic rosin was slowly added dropwise, and the reaction temperature was maintained at 80°C to 100°C for 2 hours. After the reaction was completed, it was cooled to room temperature, 100mL of anhydrous ethanol solvent was added, and the reaction product was washed to remove unreacted substances and by-products to obtain a maleic rosin modified polyether macromonomer.

[0057] 3. Preparation of water reducing agent

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

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

[0060] Wherein, liquid A: 14g acrylic acid + 15g deionized water;

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

[0062] Example 2

[0063] 1. Preparation of modified maleic rosin

[0064] S110, dissolving 10 g of maleic rosin in 50 mL of dichloromethane, and stirring evenly at 80° C. to obtain a maleic rosin solution;

[0065] S120, adding 0.2 g of p-toluenesulfonic acid to the maleic rosin solution, and continuing to stir until it is completely dissolved to obtain a mixed solution;

[0066] S130, slowly drop 6 g of epichlorohydrin within 30 min, maintain the reaction temperature, and continue stirring the reaction for 2 hours to generate modified maleic rosin.

[0067] 2. Preparation of maleic rosin modified polyether macromonomer

[0068] 40g of ethylene glycol monovinyl polyglycol ether (molecular weight 2400) was heated to a molten state (about 80°C), and then 15g of modified maleic rosin was slowly added dropwise, and the reaction temperature was maintained at 80°C to 100°C for 2 hours. After the reaction was completed, it was cooled to room temperature, 100mL of anhydrous ethanol solvent was added, and the reaction product was washed to remove unreacted substances and by-products to obtain a maleic rosin modified polyether macromonomer.

[0069] 3. Preparation of water reducing agent

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

[0071] S220, at room temperature, liquid A and liquid B are added dropwise simultaneously, the dropwise addition time of liquid A is 1 hour, and the dropwise addition time of liquid B is 1 hour. After the dropwise 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 obtain the water reducing agent.

[0072] Wherein, liquid A: 14g acrylic acid + 15g deionized water;

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

[0074] Example 3

[0075] 1. Preparation of modified maleic rosin

[0076] S110, dissolving 10 g of maleic rosin in 50 mL of anhydrous toluene, stirring evenly at 70° C. to obtain a maleic rosin solution;

[0077] S120, adding 0.2 g of p-toluenesulfonic acid to the maleic rosin solution, and continuing to stir until it is completely dissolved to obtain a mixed solution;

[0078] S130, slowly drop 6 g of epichlorohydrin within 30 min, maintain the reaction temperature, and continue stirring the reaction for 2 hours to generate modified maleic rosin.

[0079] 2. Preparation of maleic rosin modified polyether macromonomer

[0080] 40g of ethylene glycol monovinyl polyglycol ether (molecular weight 2400) was heated to a molten state (about 80°C), and then 10g of modified maleic rosin was slowly added dropwise, and the reaction temperature was maintained at 80°C to 100°C for 2 hours. After the reaction was completed, it was cooled to room temperature, 100mL of anhydrous ethanol solvent was added, and the reaction product was washed to remove unreacted substances and by-products to obtain a maleic rosin modified polyether macromonomer.

[0081] 3. Preparation of water reducing agent

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

[0083] S220, at room temperature, liquid A and liquid B are added dropwise simultaneously for 1 hour. 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 obtain the water reducing agent.

[0084] Wherein, liquid A: 18g acrylic acid + 15g deionized water;

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

[0086] Comparative Example 1

[0087] The other steps are the same as those 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 ethylene glycol monovinyl polyethylene glycol ether (molecular weight 3000) in equal amounts, 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 those in Example 1, except that when preparing the water reducer, the maleic rosin-modified polyether macromonomer is replaced with isopentyl polyoxyethylene ether, and the solid content of the prepared water reducer remains the same as that in Example 1.

[0090] Comparative Example 3

[0091] The other steps are the same as those in Example 1, excluding the step of preparing modified maleic rosin. When preparing the maleic rosin-modified polyether macromonomer, the modified maleic rosin is replaced with an equal amount of maleic rosin, and the solid content of the prepared water reducer remains the same as that in Example 1.

[0092] Comparative Example 4

[0093] The commercially available air-entraining polycarboxylate water reducer PCE-YQ has the same solid content as the water reducer prepared in Example 1.

[0094] Minfu P.042.5 cement was used to test the slump of concrete. The concrete mix ratio design for the test referred to JGJ55 "Ordinary Concrete Mix Design Code", and the concrete mix ratio is shown in Table 1. The concrete performance test referred to GB / T50080-2016 "Ordinary Concrete Mixture Performance Test Method", and the test data is shown in Table 2.

[0095] Table 1 Concrete mix ratio / m 3

[0096] Strength level Cement / kg Machine-made sand / kg Crushed stone (10-20mm) / kg Water / kg C30 360 840 1020 175

[0097] Table 2 Performance test results

[0098] sample Solid content / % 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] It can be seen from Table 2 that the product of the embodiment has a high water reduction rate and excellent air entraining performance, and while introducing bubbles, it has little effect on the strength of concrete, and its performance is significantly better than that of commercially available air-entraining water-reducing agents, indicating that when the maleic rosin-modified polyether macromonomer synthetic water-reducing agent mentioned in the invention is used, the air entraining performance and dispersibility of the water-reducing agent can be significantly improved.

[0100] 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. A maleic rosin modified polyether macromonomer, characterized in that: The raw materials for preparing the maleic rosin modified polyether macromonomer include, by weight: 40-50 parts of unsaturated polyether; 10-20 parts of modified maleic rosin; Wherein, in parts by weight, the raw materials for preparing the modified maleic rosin include: 10-20 parts of Malay rosin; 5-10 parts of epichlorohydrin and / or propylene oxide; Catalyst 0.1-0.5 parts.

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

3. A method for preparing a maleated rosin modified polyether macromonomer as claimed in claims 1 to 2, characterized in that: Includes steps: The modified maleic rosin is added dropwise into molten ethylene glycol monovinyl polyethylene glycol ether for reaction, and after the reaction is completed, a maleic rosin modified polyether macromonomer is obtained.

4. The method for preparing the maleated rosin modified polyether macromonomer according to claim 3, characterized in that: The preparation steps of the modified maleic rosin include: dissolving maleic rosin in a solvent to obtain a maleic rosin solution; Adding a catalyst to the maleic rosin solution, stirring and dissolving to obtain a mixed solution; Epichlorohydrin is added dropwise to the mixed solution for reaction. After the reaction is completed, modified maleic rosin is obtained.

5. The method for preparing the maleated rosin modified polyether macromonomer according to claim 4, characterized in that: In the step of adding epichlorohydrin dropwise to the mixed solution for reaction, the reaction time is 2 h to 3 h.

6. The method for preparing the maleated rosin modified polyether macromonomer according to claim 4, characterized in that: When epichlorohydrin is added dropwise to the mixed solution for reaction, the reaction temperature is 60°C to 80°C.

7. The method for preparing the maleated 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 described in any one of claims 1 to 2.

9. A method for preparing a water reducing agent as claimed in claim 8, characterized in that: The raw materials for preparing the water reducing agent include:

10. A method for preparing a water reducing agent as claimed in claim 8, characterized in that: Includes steps: Mixing maleic rosin modified polyether macromonomer, unsaturated acid, oxidant and water to obtain a mother solution; Add solution A and solution B dropwise to the mother solution, 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 water reducing agent; Wherein, liquid A is a mixture of unsaturated acid 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; Liquid B is an aqueous solution of a reducing agent and a chain transfer agent.

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