A high-broad-spectrum polycarboxylate water-reducing agent mother liquor and its preparation process

Abstract

The present application relates to the technical field of water reducing agent preparation, and in particular to a high-broad-spectrum polycarboxylic acid water reducing agent mother solution and its preparation process. The polycarboxylic acid water reducing agent mother solution is obtained by copolymerizing olefin functional monomers, sulfonic acid functional monomers and acrylic acid, and has good air entraining property and good foam stabilizing effect, can improve the slump retention performance of the polycarboxylic acid water reducing agent mother solution, reduce the slump loss rate of concrete, and has good compressive strength.

Description

Technical Field

[0001] The present application belongs to the technical field of water reducing agent preparation, and in particular relates to a high-broad-spectrum polycarboxylic acid water reducing agent mother solution and a preparation process thereof. Background Art

[0002] Concrete is a composite material composed of cementitious medium and aggregate particles and fragments. It is favored by engineers because of its low price, easy availability, good water resistance, plasticity and fluidity, and has become one of the most important materials in the civil engineering industry. With the progress of science and the development of the times, the utilization rate of concrete is constantly increasing, and the performance requirements of concrete are getting higher and higher. As a new type of high-performance water reducer, polycarboxylate water reducer has a series of outstanding properties such as low dosage, high water reduction rate, good slump retention, small shrinkage, relatively good adaptability to cement and admixtures, and obvious reinforcement effect. At the same time, the production process is environmentally friendly and has been widely used in various engineering fields. Due to the slow modernization process in my country in the last century, the lack of raw materials, and the backward production equipment, the recognition and application of polycarboxylate water reducers were relatively late. Although there have been a lot of achievements in the research on the dispersing mechanism of polycarboxylate water reducers, the emergence of more and more new types of concrete has made the composition of concrete more complicated, the amount of concrete with a single cementitious material has dropped significantly, and more and more admixtures are used in concrete preparation. In response to demands for higher performance of concrete, more complex raw materials, and the use of low-quality raw materials, there are further requirements for improving the performance of polycarboxylic acid water-reducing agents.

[0003] The Chinese patent with announcement number CN118359397B discloses a high-workability polycarboxylate water-reducing agent and a preparation method thereof. The polycarboxylate water-reducing agent with good dispersion fluidity is prepared using homemade polycarboxylate water-reducing agent mother liquor, foam stabilizer, defoamer, expander and water as raw materials. The silane group in the di(disilyl)amine contained in the polycarboxylate water-reducing agent can polymerize with calcium ions and aluminum ions to produce a network structure that protects bubbles and prevents bubbles from bursting too quickly. At the same time, the organosilane will generate silicate gel in the cement slurry, which can absorb and retain water, avoid water loss in the cement, and have the effect of water retention and thickening. The Chinese patent with the announcement number CN109796561B discloses an aromatic ring polycarboxylate water-reducing agent mother liquor and its preparation method and application, which is prepared by the quaternary copolymerization reaction of aromatic conjugated unsaturated carboxylic acid, unsaturated functional monomer, unsaturated fatty carboxylic acid and isopentenyl polyoxyethylene ether macromonomer. The water-reducing agent prepared by the mother liquor has antibacterial and antiseptic effects, and does not need to add a large amount of antiseptic and bactericide. At the same time, the aromatic group has a large steric hindrance, which can effectively slow down the initial release of carboxyl groups of the water-reducing agent and the adsorption of cement particles, thereby playing a slow release role and enhancing the slump retention capacity of concrete. However, the above-mentioned polycarboxylate water-reducing agent directly mixes the raw materials during the preparation process, and there is a problem of uneven dispersion between the raw materials, which affects the performance of the polycarboxylate water-reducing agent. Summary of the invention

[0004] In order to solve the above technical problems, the present invention provides a high-broad-spectrum polycarboxylate water-reducing agent mother liquor and a preparation process thereof. The polycarboxylate water-reducing agent mother liquor is obtained by copolymerizing olefin functional monomers, sulfonic acid functional monomers and acrylic acid. The polycarboxylate water-reducing agent mother liquor has good air entraining property and good foam stabilizing effect, can improve the slump retention performance of the polycarboxylate water-reducing agent mother liquor, reduce the slump loss rate of concrete, and has good compressive strength.

[0005] The technical solution adopted by the present invention to solve the above technical problems is as follows:

[0006] A preparation process of a high-broad-spectrum polycarboxylate water-reducing agent mother solution comprises the following steps:

[0007] S100, using raw materials including non-ionic cellulose ether, sulfonylating agent, alcohol amine compound, and ester compound, and obtaining olefin functional monomers through sulfonylation, amino substitution, and epoxy addition;

[0008] S200, using raw materials including unsaturated fatty alcohol, epoxy compound and sulfite, and obtaining sulfonic acid functional monomers through epoxy addition and nucleophilic substitution;

[0009] S300, olefin functional monomers, sulfonic acid functional monomers and acrylic acid are copolymerized to obtain the polycarboxylic acid water-reducing agent mother solution.

[0010] Concrete admixtures can effectively improve and adjust the performance of concrete. As a type of concrete admixture, water reducer is an admixture that can minimize the amount of water required when mixing concrete while maintaining other properties such as concrete slump. Polycarboxylic acid water reducer is a water reducer with good performance and is widely used. However, with rapid development, existing polycarboxylic acid water reducers are difficult to adapt to the diversified construction needs of engineering application fields. Therefore, in the present invention, the synthetic monomers of polycarboxylic acid water reducer are modified to obtain ionic cellulose ether-modified olefin functional monomers and sulfonated sulfonic acid functional monomers, so that it has more excellent performance.

[0011] Furthermore, S100 specifically includes:

[0012] S110, add NaOH solution to the hydroxymethyl cellulose ether solution, stir at room temperature for 2-5h, then add p-toluenesulfonyl chloride, react at 3-8°C for 3-5h, filter and adjust the pH to 6-7 with hydrochloric acid, take the filtrate and refrigerate at 3-8°C for 8-12h, then filter and take the precipitate, recrystallize in deionized water for 3-5 times, and dry in a vacuum drying oven at 50-60°C for 28-32h to obtain a white solid; wherein the preparation method of the hydroxymethyl cellulose ether solution is: in deionized water Add hydroxymethyl cellulose ether, stir for 15-30 minutes, then raise the temperature to 65-75°C and continue stirring for 20-30 minutes to obtain; the amount of hydroxymethyl cellulose ether in deionized water is 0.25-0.40 g / mL; the concentration of NaOH solution is 2 mol / L, and the concentration of hydrochloric acid is 1.2 mol / L; the volume ratio of hydroxymethyl cellulose ether solution to NaOH solution is 2.5-3.2:1; the mass ratio of hydroxymethyl cellulose ether to p-toluenesulfonyl chloride is 3-4.5:1;

[0013] S120, add white solid and ethanolamine to N,N-dimethylformamide solution, stir at 65-80°C for 6-8h, then cool to room temperature to obtain a mixed solution, precipitate with acetone at 4-8°C, dissolve in deionized water, continue to precipitate with acetone, repeat the operation 3-5 times to remove unreacted ethanolamine, and then place in a vacuum drying oven at 40-50°C to dry for 28-32h to obtain an amino-substituted product; wherein the concentration of N,N-dimethylformamide solution is 30wt%; the volume ratio of N,N-dimethylformamide solution to ethanolamine is 1-1.2:1; the amount of white solid in N,N-dimethylformamide solution is 0.36-0.52g / mL;

[0014] S130, adding the amino-substituted product and glycidyl methacrylate to an N,N-dimethylformamide solution, stirring at 75-85°C for 12-16 hours, cooling to room temperature, precipitating with acetone at 4-8°C, dissolving in deionized water, continuing precipitation with acetone, repeating the operation 3-5 times, removing unreacted glycidyl methacrylate, and drying in a vacuum drying oven at 40-50°C for 28-32 hours to obtain the olefin functional monomer; wherein the concentration of the N,N-dimethylformamide solution is 30wt%; the amount of glycidyl methacrylate in the N,N-dimethylformamide solution is 0.35-0.48g / mL; the mass ratio of the amino-substituted product to glycidyl methacrylate is 6.5-8.2:1.

[0015] The steric hindrance effect is an important reason why polycarboxylate water-reducing agent has high dispersibility, and hydroxymethyl cellulose ether also has large steric hindrance due to its long chain structure and ring structure, so in the present invention, hydroxymethyl cellulose ether is used as a raw material for modification to further improve the dispersibility of polycarboxylate water-reducing agent. The present invention uses the side chain as the modification site, and under alkaline conditions, hydroxymethyl cellulose ether undergoes a sulfonylation reaction with p-toluenesulfonyl chloride, and then uses ethanolamine to replace the amino group, and finally undergoes an epoxy ring-opening addition reaction with glycidyl methacrylate to prepare a hydroxymethyl cellulose ether-modified olefin functional monomer. Since hydroxymethyl cellulose ether has a long chain structure and a ring structure, when the water reducer is adsorbed to the surface of cement particles, the side chain will form an adsorption layer of a certain thickness. When the cement particles are close to each other, the side chain of the hydroxymethyl cellulose ether will be compressed to form a larger repulsive force, which promotes the separation between cement particles and prevents cement particles from agglomerating. In addition, the strongly hydrophilic polar groups such as hydroxyl groups on its side chains will associate with water molecules to form hydrogen bonds, forming a layer of solvated water film on the surface of cement particles, thereby improving the wettability of the cement particle surface and playing a lubricating role on the cement particle surface, making it difficult for cement particles to agglomerate. In addition, the negative The charged groups and the calcium ions on the cement particles attract each other through electrostatic interaction, so that the cement particles coated with the water reducer have electrostatic repulsion due to the same charge, which destroys the original flocculation structure of the cement concrete, causing the free water wrapped therein to be released, thereby increasing the fluidity of the cement concrete; at the same time, the functional monomer also contains nitrogen atoms, and the lone pair of electrons on the nitrogen atoms form covalent bonds with the metal cations in the cement particles through the coordination effect to form tiny soluble areas, which promotes the dispersion of hydration products; in addition, the reduction in calcium ion concentration can promote the hydration of C3S and improve the early strength.

[0016] Furthermore, S200 specifically includes:

[0017] S210, after adding a catalyst to allyl alcohol, epichlorohydrin is added dropwise at 4-8°C, and after the addition is completed, the temperature is raised to 65-80°C for reaction for 6-8h, and after the reaction is completed, the reaction is distilled under reduced pressure, and the vacuum degree is monitored with a McLaren vacuum gauge. When the vacuum degree is 3 mmHg, a fraction at 110°C is collected to obtain an intermediate; wherein the catalyst is any one or a mixture of boron trifluoride ether, trifluoromethanesulfonic anhydride, boron trifluoride, and aluminum chloride; the dripping speed of epichlorohydrin is 4-6s per drop; the volume ratio of allyl alcohol to epichlorohydrin is 1:2-2.5; the amount of the catalyst in epichlorohydrin is 0.002-0.004g / mL;

[0018] S220, adding an intermediate and an emulsifier to an anhydrous sodium sulfite aqueous solution, raising the temperature to 45-65°C to react for 4-6 hours, recrystallizing with anhydrous ethanol for 3-5 times, washing with petroleum ether for 2-3 times, placing in a vacuum drying oven at 40-50°C for 3-5 hours to obtain a sulfonic acid functional monomer; wherein the emulsifier is one or a mixture of sodium vinyl sulfonate, sodium allyl sulfonate, and 3-allyloxy-2-hydroxy-1-propane sulfonic acid sodium salt; the concentration of the anhydrous sodium sulfite aqueous solution is 40wt%; the mass ratio of anhydrous sodium sulfite, intermediate and emulsifier is 1.5-2.2:1:0.004-0.008.

[0019] Further, since the sulfonic acid functional group is an anionic functional group, it can form a double electric layer adsorption on the surface of cement particles, and improve the adsorption of cement particles to polycarboxylate water-reducing agent molecules. Therefore, in the present invention, firstly, acryl alcohol is used to react with epichlorohydrin under the catalysis of boron trifluoride ether complex to generate a ring-opening addition reaction, and then SN2 nucleophilic substitution reaction occurs with sodium sulfite to obtain a sulfonic acid functional monomer. During the use of polycarboxylate water-reducing agent, the presence of groups such as hydroxyl, carboxyl, and sulfonic acid groups can make the main chain adsorbed on the surface of cement particles to prevent the particles from contacting with water, and can provide electrostatic repulsion to combine with calcium ions to form a stable calcium-rich protective layer, while the hydroxyl groups on the side chains can be complexed with silicate hydrated ions, reduce the concentration of calcium and silicon ions, prevent the release of ions, further enhance the hindering effect between cement particles, and prevent the agglomeration between cement particles. At the same time, the presence of sulfonic acid groups can effectively improve the air entrainment of polycarboxylate water-reducing agent, and the synergistic effect with carboxyl groups can effectively improve the performance of polycarboxylate water-reducing agent.

[0020] Furthermore, S300 specifically includes:

[0021] S300, adding olefin functional monomers, sulfonic acid functional monomers and deionized water into a reactor, raising the temperature to 30-40°C and reacting for 20-40 minutes, adding an initiator, raising the temperature to 45-55°C and then dripping mercaptopropionic acid aqueous solution and acrylic acid aqueous solution, reacting at a constant temperature for 1-2 hours after the dripping is completed, adjusting the pH to 6-8 with NaOH solution after the reaction is completed, cooling to room temperature, and obtaining the polycarboxylate water-reducing agent mother liquor; wherein the initiator is ammonium persulfate; wherein the mass ratio of olefin functional monomers, sulfonic acid functional monomers and acrylic acid is 2.4-3.6:2.0-3.2:1; the volume ratio of deionized water, mercaptopropionic acid aqueous solution and acrylic acid aqueous solution is 1:0.5-0.8:1.2-1.5; the concentration of mercaptopropionic acid aqueous solution is 0.1 mol / L, the concentration of acrylic acid aqueous solution is 0.2 mol / L, and the concentration of NaOH solution is 2 mol / L.

[0022] The present invention also provides a high-broad-spectrum polycarboxylate water-reducing agent mother solution, which is obtained by using the preparation process of the high-broad-spectrum polycarboxylate water-reducing agent mother solution as described in any of the above technical solutions.

[0023] The present invention has the following beneficial effects:

[0024] The present invention uses the side chain as the modification site, and under alkaline conditions, hydroxymethyl cellulose ether undergoes sulfonylation reaction with p-toluenesulfonyl chloride, and then uses ethanolamine to replace the amino group, and finally undergoes epoxy ring-opening addition reaction with glycidyl methacrylate to prepare hydroxymethyl cellulose ether modified olefin functional monomers; acryl alcohol is used to undergo ring-opening addition reaction with epichlorohydrin under the catalysis of boron trifluoride ether complex, and then undergoes SN2 nucleophilic substitution reaction with sodium sulfite to obtain sulfonic acid functional monomers; the presence of the long chain structure and cyclic structure of hydroxymethyl cellulose ether can form an adsorption layer of a certain thickness when the water reducer is adsorbed on the surface of cement particles, thereby promoting the separation between cement particles. At the same time, the presence of strong polar groups on the water reducer molecular chain can associate with water molecules to form hydrogen bonds, form a solvated water film on the surface of cement particles, improve the wettability of the cement particle surface, prevent the agglomeration between cement particles, and thus increase the fluidity of cement concrete. DETAILED DESCRIPTION

[0025] The following will be combined with the embodiments of the present application to clearly and completely describe the technical solutions in the embodiments of the present application. Obviously, the described embodiments are only part of the embodiments of the present application, not all of the embodiments. Based on the embodiments in the present application, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of this application.

[0026] The hydroxymethyl cellulose ether (industrial grade, Viscosity (mPa·s): 400, MS (Methyl): 1.8-2.0, MS (Hydroxypropyl): 0.2-0.3) used in the present invention was purchased from Shanghai Chenqi Chemical Technology Co., Ltd., p-toluenesulfonyl chloride (chemically pure), ethanolamine (AR), and glycidyl methacrylate (≥97%, containing 100ppm MEHQ stabilizer) were all purchased from Shanghai Aladdin Biochemical Technology Co., Ltd., allyl alcohol (Shanghai test), epichlorohydrin (AR), anhydrous sodium sulfate (98%), and acrylic acid (AR) were all purchased from Sinopharm Chemical Reagent Co., Ltd., and all reagents were commercially available.

[0027] Embodiment 1

[0028] A preparation process of a high-broad-spectrum polycarboxylate water-reducing agent mother solution comprises the following steps:

[0029] S100, using raw materials including non-ionic cellulose ether, sulfonylating agent, alcohol amine compound, and ester compound, and obtaining olefin functional monomers through sulfonylation, amino substitution, and epoxy addition;

[0030] S200, using raw materials including unsaturated fatty alcohol, epoxy compound and sulfite, and obtaining sulfonic acid functional monomers through epoxy addition and nucleophilic substitution;

[0031] S300, olefin functional monomers, sulfonic acid functional monomers and acrylic acid are copolymerized to obtain the polycarboxylic acid water-reducing agent mother solution.

[0032] Among them, S100 specifically includes:

[0033] S110. Add NaOH solution to the hydroxymethyl cellulose ether solution, stir at room temperature for 3 hours, then add p-toluenesulfonyl chloride, react at 5°C for 4 hours, filter and adjust the pH to 6-7 with hydrochloric acid, take the filtrate and refrigerate at 5°C for 10 hours, then filter and take the precipitate, recrystallize it in deionized water for 5 times, and dry it in a vacuum drying oven at 55°C for 30 hours to obtain a white solid; wherein the preparation method of the hydroxymethyl cellulose ether solution is: add hydroxymethyl cellulose ether to deionized water, stir for 20 minutes, then raise the temperature to 70°C and continue stirring for 30 minutes to obtain; the amount of hydroxymethyl cellulose ether in deionized water is 0.32 g / mL; the concentration of NaOH solution is 2 mol / L, and the concentration of hydrochloric acid is 1.2 mol / L; the volume ratio of hydroxymethyl cellulose ether solution to NaOH solution is 3.0:1; the mass ratio of hydroxymethyl cellulose ether to p-toluenesulfonyl chloride is 3.5:1;

[0034] S120, add white solid and ethanolamine to N,N-dimethylformamide solution, stir at 75°C for 7h, and then cool to room temperature to obtain a mixed solution, precipitate with acetone at 5°C, dissolve in deionized water, continue to precipitate with acetone, repeat the operation 5 times to remove unreacted ethanolamine, and then place in a vacuum drying oven at 45°C for 30h to obtain an amino-substituted product; wherein the concentration of N,N-dimethylformamide solution is 30wt%; the volume ratio of N,N-dimethylformamide solution to ethanolamine is 1.2:1; the amount of white solid in N,N-dimethylformamide solution is 0.48g / mL;

[0035] S130. Add the amino-substituted product and glycidyl methacrylate to an N,N-dimethylformamide solution, stir at 80°C for 14 hours, cool to room temperature, precipitate with acetone at 5°C, dissolve in deionized water, continue to precipitate with acetone, repeat the operation 5 times, remove the unreacted glycidyl methacrylate, and dry in a vacuum drying oven at 45°C for 30 hours to obtain an olefin functional monomer; wherein the concentration of the N,N-dimethylformamide solution is 30wt%; the amount of glycidyl methacrylate in the N,N-dimethylformamide solution is 0.42g / mL; the mass ratio of the amino-substituted product to glycidyl methacrylate is 7.8:1.

[0036] Among them, S200 specifically includes:

[0037] S210, after adding boron trifluoride ether catalyst to allyl alcohol, epichlorohydrin was added dropwise at 5°C, the temperature was raised to 75°C after the addition was completed, the reaction was carried out for 8 hours, and distillation was carried out under reduced pressure after the reaction was completed. The vacuum degree was monitored with a McLaren vacuum gauge, and the fraction at 110°C was collected when the vacuum degree was 3 mmHg to obtain an intermediate; wherein the dropwise addition speed of epichlorohydrin was 4-6s per drop; the volume ratio of allyl alcohol to epichlorohydrin was 1:2.2; the amount of the catalyst in epichlorohydrin was 0.004 g / mL;

[0038] S220, adding the intermediate and the emulsifier sodium vinyl sulfonate to an anhydrous sodium sulfite aqueous solution, raising the temperature to 55°C for reaction for 6 hours, recrystallizing with anhydrous ethanol for 5 times, washing with petroleum ether for 3 times, placing in a vacuum drying oven at 45°C for 5 hours to obtain a sulfonic acid functional monomer; wherein the concentration of the anhydrous sodium sulfite aqueous solution is 40wt%; and the mass ratio of anhydrous sodium sulfite, the intermediate and the emulsifier is 1.8:1:0.006;

[0039] Among them, S300 specifically includes:

[0040] S300, adding olefin functional monomers, sulfonic acid functional monomers and deionized water into a reactor, raising the temperature to 35°C and reacting for 30 minutes, adding initiator ammonium persulfate, raising the temperature to 50°C and then dropping mercaptopropionic acid aqueous solution and acrylic acid aqueous solution, after the dropwise addition is completed, reacting at a constant temperature for 2 hours, adjusting the pH to 6-8 with NaOH solution after the reaction is completed, cooling to room temperature, and obtaining a polycarboxylic acid water-reducing agent mother liquor; wherein, the mass ratio of olefin functional monomers, sulfonic acid functional monomers and acrylic acid is 3.2:2.4:1; the volume ratio of deionized water, mercaptopropionic acid aqueous solution and acrylic acid aqueous solution is 1:0.6:1.4; the concentration of mercaptopropionic acid aqueous solution is 0.1 mol / L, the concentration of acrylic acid aqueous solution is 0.2 mol / L, and the concentration of NaOH solution is 2 mol / L.

[0041] Embodiment 2

[0042] This embodiment is different from the first embodiment in the following aspects:

[0043] In step S110, after adding NaOH solution to the hydroxymethyl cellulose ether solution, stirring at room temperature for 2 hours, then adding p-toluenesulfonyl chloride, reacting at 3°C ​​for 3 hours, taking the filtrate and refrigerating it at 3°C ​​for 8 hours, and then filtering out the precipitate, recrystallizing it in deionized water for 3 times, and drying it in a vacuum drying oven at 50°C for 28 hours; the amount of hydroxymethyl cellulose ether in deionized water is 0.25 g / mL; the volume ratio of hydroxymethyl cellulose ether solution to NaOH solution is 2.5:1; the mass ratio of hydroxymethyl cellulose ether to p-toluenesulfonyl chloride is 3:1.

[0044] In step S120, a white solid and ethanolamine are added to an N,N-dimethylformamide solution, and the mixture is stirred at 65° C. for 6 hours and then cooled to room temperature to obtain a mixed solution, which is precipitated with acetone at 4° C., dissolved in deionized water, and further precipitated with acetone. The operation is repeated 3 times and the mixture is placed in a vacuum drying oven and dried at 40° C. for 32 hours; the volume ratio of the N,N-dimethylformamide solution to ethanolamine is 1:1; and the amount of the white solid in the N,N-dimethylformamide solution is 0.36 g / mL.

[0045] In step S130, the amino-substituted product and glycidyl methacrylate are added to the N,N-dimethylformamide solution, stirred at 75°C for 16 hours, cooled to room temperature, precipitated with acetone at 4°C, dissolved in deionized water, and precipitated with acetone again. The operation is repeated 3 times, and the solution is placed in a vacuum drying oven at 40°C for 32 hours. The amount of glycidyl methacrylate in the N,N-dimethylformamide solution is 0.35 g / mL; the mass ratio of the amino-substituted product to glycidyl methacrylate is 6.5:1.

[0046] In step S210, after adding boron trifluoride etherate as a catalyst to allyl alcohol, epichlorohydrin is added dropwise at 4° C., and after the addition is completed, the temperature is raised to 65° C. and the reaction is carried out for 8 hours; the volume ratio of allyl alcohol to epichlorohydrin is 1:2; and the amount of the catalyst in epichlorohydrin is 0.002 g / mL.

[0047] In step S220, the intermediate and the emulsifier sodium vinyl sulfonate are added to the anhydrous sodium sulfite aqueous solution, the temperature is raised to 45°C for reaction for 4 hours, and the mixture is recrystallized with anhydrous ethanol for 3 times, washed with petroleum ether for 2 times, and dried in a vacuum drying oven at 40°C for 5 hours to obtain a sulfonic acid functional monomer; the mass ratio of anhydrous sodium sulfite, the intermediate and the emulsifier is 1.5:1:0.004.

[0048] In step S300, olefin functional monomers, sulfonic acid functional monomers and deionized water are added to the reactor, the temperature is raised to 30°C and the reaction is carried out for 20 minutes, ammonium persulfate as an initiator is added, the temperature is raised to 45°C and then an aqueous solution of mercaptopropionic acid and an aqueous solution of acrylic acid are added dropwise, and the reaction is carried out at a constant temperature for 2 hours; the mass ratio of the olefin functional monomers, the sulfonic acid functional monomers and acrylic acid is 2.4:2.0:1; the volume ratio of deionized water, the aqueous solution of mercaptopropionic acid and the aqueous solution of acrylic acid is 1:0.5:1.2.

[0049] The rest is as per Example 1.

[0050] Embodiment 3

[0051] This embodiment is different from the first embodiment in the following aspects:

[0052] In step S110, after adding NaOH solution to the hydroxymethyl cellulose ether solution, stirring at room temperature for 5 hours, then adding p-toluenesulfonyl chloride, reacting at 8° C. for 5 hours, taking the filtrate and refrigerating it at 8° C. for 12 hours, and then filtering out the precipitate, recrystallizing it in deionized water for 5 times, and drying it in a vacuum drying oven at 60° C. for 32 hours; the amount of hydroxymethyl cellulose ether in deionized water is 0.40 g / mL; the volume ratio of hydroxymethyl cellulose ether solution to NaOH solution is 3.2:1; the mass ratio of hydroxymethyl cellulose ether to p-toluenesulfonyl chloride is 4.5:1.

[0053] In step S120, a white solid and ethanolamine are added to an N,N-dimethylformamide solution, and the mixture is stirred at 80° C. for 8 h and then cooled to room temperature to obtain a mixed solution, which is precipitated with acetone at 8° C., dissolved in deionized water, and further precipitated with acetone. The operation is repeated 5 times and the mixture is placed in a vacuum drying oven and dried at 50° C. for 32 h; the volume ratio of the N,N-dimethylformamide solution to ethanolamine is 1.2:1; and the amount of the white solid in the N,N-dimethylformamide solution is 0.52 g / mL.

[0054] In step S130, the amino-substituted product and glycidyl methacrylate are added to the N,N-dimethylformamide solution, stirred at 85°C for 16 hours, cooled to room temperature, precipitated with acetone at 8°C, dissolved in deionized water, and precipitated with acetone again. The operation is repeated 5 times, and the solution is placed in a vacuum drying oven at 50°C for 28 hours. The amount of glycidyl methacrylate in the N,N-dimethylformamide solution is 0.48 g / mL; the mass ratio of the amino-substituted product to glycidyl methacrylate is 8.2:1.

[0055] In step S210, after adding boron trifluoride etherate as a catalyst to allyl alcohol, epichlorohydrin is added dropwise at 8° C., and after the addition is completed, the temperature is raised to 80° C. and the reaction is carried out for 8 hours; the volume ratio of allyl alcohol to epichlorohydrin is 1:2.5; and the amount of the catalyst in epichlorohydrin is 0.004 g / mL.

[0056] In step S220, the intermediate and the emulsifier sodium vinyl sulfonate are added to the anhydrous sodium sulfite aqueous solution, the temperature is raised to 65°C for reaction for 6 hours, and the mixture is recrystallized with anhydrous ethanol for 5 times, washed with petroleum ether for 3 times, and dried in a vacuum drying oven at 50°C for 3 hours to obtain a sulfonic acid functional monomer; the mass ratio of anhydrous sodium sulfite, the intermediate and the emulsifier is 2.2:1:0.008.

[0057] In step S300, olefin functional monomers, sulfonic acid functional monomers and deionized water are added to the reactor, the temperature is raised to 40°C and the reaction is carried out for 40 minutes, and then ammonium persulfate as an initiator is added, the temperature is raised to 55°C, and then an aqueous solution of mercaptopropionic acid and an aqueous solution of acrylic acid are added dropwise, and the reaction is carried out at a constant temperature for 2 hours; the mass ratio of the olefin functional monomers, the sulfonic acid functional monomers and acrylic acid is 3.6:3.2:1; the volume ratio of deionized water, the aqueous solution of mercaptopropionic acid and the aqueous solution of acrylic acid is 1:0.8:1.5.

[0058] The rest is as per Example 1.

[0059] Comparative Example 1

[0060] Compared with Example 1, this comparative example replaces the olefin functional monomer with glycidyl methacrylate and hydroxymethyl cellulose ether, and the rest is the same as Example 1, specifically:

[0061] A preparation process of a high-broad-spectrum polycarboxylate water-reducing agent mother liquor comprises the following steps: adding glycidyl methacrylate, hydroxymethyl cellulose ether, sulfonic acid functional monomer and deionized water into a reactor, raising the temperature to 35°C and reacting for 30 minutes, adding an initiator ammonium persulfate, raising the temperature to 50°C and then dripping mercaptopropionic acid aqueous solution and acrylic acid aqueous solution, reacting at a constant temperature for 2 hours after the dripping is completed, adjusting the pH to 6-8 with a NaOH solution after the reaction is completed, cooling to room temperature, and obtaining a polycarboxylate water-reducing agent mother liquor; wherein the mass ratio of glycidyl methacrylate, hydroxymethyl cellulose ether, sulfonic acid functional monomer and acrylic acid is 2.0:1.2:2.4:1; the volume ratio of deionized water, mercaptopropionic acid aqueous solution and acrylic acid aqueous solution is 1:0.6:1.4; the concentration of mercaptopropionic acid aqueous solution is 0.1 mol / L, the concentration of acrylic acid aqueous solution is 0.2 mol / L, and the concentration of NaOH solution is 2 mol / L.

[0062] Comparative Example 2

[0063] Compared with Example 1, this comparative example replaces the olefin functional monomer with glycidyl methacrylate, and the rest is referred to Example 1, specifically:

[0064] A preparation process of a high-broad-spectrum polycarboxylate water-reducing agent mother liquor comprises the following steps: adding glycidyl methacrylate, sulfonic acid functional monomers and deionized water into a reactor, raising the temperature to 35°C and reacting for 30 minutes, adding an initiator ammonium persulfate, raising the temperature to 50°C and then dripping mercaptopropionic acid aqueous solution and acrylic acid aqueous solution, reacting at a constant temperature for 2 hours after the dripping is completed, adjusting the pH to 6-8 with a NaOH solution after the reaction is completed, cooling to room temperature, and obtaining a polycarboxylate water-reducing agent mother liquor; wherein the mass ratio of glycidyl methacrylate, sulfonic acid functional monomers and acrylic acid is 3.2:2.4:1; the volume ratio of deionized water, mercaptopropionic acid aqueous solution and acrylic acid aqueous solution is 1:0.6:1.4; the concentration of the mercaptopropionic acid aqueous solution is 0.1 mol / L, the concentration of the acrylic acid aqueous solution is 0.2 mol / L, and the concentration of the NaOH solution is 2 mol / L.

[0065] Comparative Example 3

[0066] Compared with Example 1, the sulfonic acid functional monomer in this comparative example is replaced with propylene alcohol, and the rest is referred to Example 1, specifically:

[0067] A preparation process of a high-broad-spectrum polycarboxylate water-reducing agent mother liquor comprises the following steps: adding olefin functional monomers, acryl alcohol and deionized water into a reactor, raising the temperature to 35°C and reacting for 30 minutes, adding an initiator ammonium persulfate, raising the temperature to 50°C and then dripping mercaptopropionic acid aqueous solution and acrylic acid aqueous solution, reacting at a constant temperature for 2 hours after the dripping is completed, adjusting the pH to 6-8 with a NaOH solution after the reaction is completed, cooling to room temperature, and obtaining a polycarboxylate water-reducing agent mother liquor; wherein the mass ratio of the olefin functional monomers, acryl alcohol and acrylic acid is 3.2:2.4:1; the volume ratio of deionized water, mercaptopropionic acid aqueous solution and acrylic acid aqueous solution is 1:0.6:1.4; the concentration of the mercaptopropionic acid aqueous solution is 0.1 mol / L, the concentration of the acrylic acid aqueous solution is 0.2 mol / L, and the concentration of the NaOH solution is 2 mol / L.

[0068] Comparative Example 4

[0069] Compared with Example 1, this comparative example replaces the olefin functional monomer with glycidyl methacrylate, and replaces the sulfonic acid functional monomer with acryl alcohol. The rest is the same as Example 1, specifically:

[0070] A preparation process of a high-broad-spectrum polycarboxylate water-reducing agent mother liquor comprises the following steps: adding glycidyl methacrylate, acryl alcohol and deionized water into a reactor, raising the temperature to 35°C and reacting for 30 minutes, adding an initiator ammonium persulfate, raising the temperature to 50°C and then dripping a mercaptopropionic acid aqueous solution and an acrylic acid aqueous solution, reacting at a constant temperature for 2 hours after the dripping is completed, adjusting the pH to 6-8 with a NaOH solution after the reaction is completed, cooling to room temperature, and obtaining a polycarboxylate water-reducing agent mother liquor; wherein the mass ratio of glycidyl methacrylate, acryl alcohol and acrylic acid is 3.2:2.4:1; the volume ratio of deionized water, mercaptopropionic acid aqueous solution and acrylic acid aqueous solution is 1:0.6:1.4; the concentration of the mercaptopropionic acid aqueous solution is 0.1 mol / L, the concentration of the acrylic acid aqueous solution is 0.2 mol / L, and the concentration of the NaOH solution is 2 mol / L.

[0071] Related tests:

[0072] The polycarboxylate water-reducing agent mother solutions prepared in Examples 1 to 3 and Comparative Examples 1 to 4 were used in ordinary C30 concrete, and the initial slump, slump after time, air content, compressive strength at various ages and other indicators of the concrete were tested when the water-reducing agent mother solution was added in a solid content of 0.18%.

[0073] The cement used in the experiment is Conch 42.5 ordinary Portland cement (Liquan), and the amount of water used is to make the initial slump of the concrete reach 210±10mm. Referring to the test standard GB / 8076-2008 "Concrete Admixtures", the test results are shown in Table 1.

[0074] Table 1 Performance test results

[0075]

[0076]

[0077] It can be seen from the test results in Table 1 that the relevant properties of the polycarboxylate water-reducing agent mother solutions prepared in Examples 1 to 3 are better than those in Comparative Examples 1 to 4, and in particular, Example 1 has the best effect. It can be seen from the test results that the water-reducing agent mother solution prepared in Example 1 has good air entrainment and good foam stabilization effect, can improve the slump retention performance of the polycarboxylate water-reducing agent mother solution, reduce the slump loss rate of concrete, and has good compressive strength.

[0078] It should be noted that, in this article, relational terms such as first and second, etc. are only used to distinguish one entity or operation from another entity or operation, and do not necessarily require or imply any such actual relationship or order between these entities or operations. Moreover, the terms "include", "comprise" or any other variants thereof are intended to cover non-exclusive inclusion, so that a process, method, article or device including a series of elements includes not only those elements, but also other elements not explicitly listed, or also includes elements inherent to such process, method, article or device.

[0079] Although the embodiments of the present application have been shown and described, it will be appreciated by those skilled in the art that various changes, modifications, substitutions and variations may be made to the embodiments without departing from the principles and spirit of the present application, and that the scope of the present application is defined by the appended claims and their equivalents.

Claims

1. A process for preparing a high-broad-spectrum polycarboxylate water-reducing agent mother solution, characterized in that: The following steps are involved: S100, using raw materials including non-ionic cellulose ether, sulfonylating agent, alcohol amine compound, and ester compound, and obtaining olefin functional monomers through sulfonylation, amino substitution, and epoxy addition; S200, using raw materials including unsaturated fatty alcohol, epoxy compound and sulfite, and obtaining sulfonic acid functional monomers through epoxy addition and nucleophilic substitution; S300, olefin functional monomers, sulfonic acid functional monomers and acrylic acid are copolymerized to obtain the polycarboxylate water-reducing agent mother solution; S100 specifically includes: S110, adding NaOH solution to the hydroxymethyl cellulose ether solution, stirring at room temperature for 2-5 hours, then adding p-toluenesulfonyl chloride, reacting at 3-8°C for 3-5 hours, adjusting the pH to 6-7 after filtering, taking the filtrate and refrigerating it at 3-8°C for 8-12 hours, filtering it with suction, recrystallizing it, and drying it to obtain a white solid; S120, adding white solid and ethanolamine to N,N-dimethylformamide solution, stirring at 65-80° C. for 6-8 hours and then cooling to room temperature to obtain a mixed solution, precipitating with acetone, and drying to obtain an amino-substituted product; S130, adding the amino-substituted product and glycidyl methacrylate to the N,N-dimethylformamide solution, stirring at 75-85° C. for 12-16 hours, cooling to room temperature, and obtaining the olefin functional monomer after precipitation with acetone and drying; S200 specifically includes: S210, after adding a catalyst to allyl alcohol, epichlorohydrin is added dropwise at 4-8°C, after the addition is completed, the temperature is raised to 65-80°C for reaction for 6-8h, after the reaction is completed, distillation is performed under reduced pressure to obtain an intermediate; S220, adding the intermediate and the emulsifier to an anhydrous sodium sulfite aqueous solution, raising the temperature to 45-65° C. to react for 4-6 hours, and obtaining a sulfonic acid functional monomer after recrystallization, washing and drying.

2. The process for preparing the high-broad-spectrum polycarboxylate water-reducing agent mother solution according to claim 1, characterized in that: In step S110, the preparation method of the hydroxymethyl cellulose ether solution is: add hydroxymethyl cellulose ether into deionized water, stir for 15-30 minutes, then raise the temperature to 65-75° C. and continue stirring for 20-30 minutes.

3. The process for preparing the mother solution of high-broad-spectrum polycarboxylate water-reducing agent according to claim 1, characterized in that: In step S210, the catalyst is any one of boron trifluoride etherate, trifluoromethanesulfonic anhydride, boron trifluoride, and aluminum chloride, or a mixture of several of them.

4. The process for preparing the high-broad-spectrum polycarboxylate water-reducing agent mother solution according to claim 1, characterized in that: In step S220, the emulsifier is one or a mixture of sodium vinyl sulfonate, sodium allyl sulfonate, and sodium 3-allyloxy-2-hydroxy-1-propane sulfonate.

5. The process for preparing the mother solution of polycarboxylate water-reducing agent with high broad-spectrum activity according to claim 1, characterized in that: S300 specifically includes: S300, adding olefin functional monomers, sulfonic acid functional monomers and deionized water into a reactor, raising the temperature to 30-40°C and reacting for 20-40 minutes, adding an initiator, raising the temperature to 45-55°C and then dripping mercaptopropionic acid aqueous solution and acrylic acid aqueous solution, after the dripping is completed, reacting at a constant temperature for 1-2 hours, adjusting the pH to 6-8 after the reaction is completed, cooling to room temperature, and obtaining the polycarboxylic acid water-reducing agent mother liquor.

6. The process for preparing the mother solution of polycarboxylate water-reducing agent with high broad-spectrum activity according to claim 5, characterized in that: In step S300, the mass ratio of olefin functional monomers, sulfonic acid functional monomers and acrylic acid is 2.4-3.6:2.0-3.2:1; the volume ratio of deionized water, mercaptopropionic acid aqueous solution and acrylic acid aqueous solution is 1:0.5-0.8:1.2-1.

5.

7. A high-broad-spectrum polycarboxylate water-reducing agent mother solution, characterized in that: The polycarboxylate water-reducing agent mother solution is obtained by using the preparation process of the high-broad-spectrum polycarboxylate water-reducing agent mother solution according to any one of claims 1 to 6.

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