CN112210049A - Water reducing agent suitable for high content of sandstone soil and preparation method thereof - Google Patents
Water reducing agent suitable for high content of sandstone soil and preparation method thereof Download PDFInfo
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- CN112210049A CN112210049A CN202011081145.0A CN202011081145A CN112210049A CN 112210049 A CN112210049 A CN 112210049A CN 202011081145 A CN202011081145 A CN 202011081145A CN 112210049 A CN112210049 A CN 112210049A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
- C08F283/06—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polyethers, polyoxymethylenes or polyacetals
- C08F283/065—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polyethers, polyoxymethylenes or polyacetals on to unsaturated polyethers, polyoxymethylenes or polyacetals
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B24/00—Use of organic materials as active ingredients for mortars, concrete or artificial stone, e.g. plasticisers
- C04B24/24—Macromolecular compounds
- C04B24/26—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- C04B24/2688—Copolymers containing at least three different monomers
- C04B24/2694—Copolymers containing at least three different monomers containing polyether side chains
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B40/00—Processes, in general, for influencing or modifying the properties of mortars, concrete or artificial stone compositions, e.g. their setting or hardening ability
- C04B40/0028—Aspects relating to the mixing step of the mortar preparation
- C04B40/0039—Premixtures of ingredients
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2103/00—Function or property of ingredients for mortars, concrete or artificial stone
- C04B2103/30—Water reducers, plasticisers, air-entrainers, flow improvers
- C04B2103/302—Water reducers
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Abstract
The invention belongs to the technical field of building materials, and relates to a water reducing agent suitable for high sandstone soil content. The invention also provides a preparation method of the concrete water reducing agent suitable for high content of sandstone soil. The water reducing agent suitable for high content of sandstone soil is developed, so that the polycarboxylate water reducing agent has good dispersibility and dispersion retentivity, can exert the water reducing performance of the water reducing agent, avoids overlarge viscosity of concrete mixture, low slump retentivity and low compressive strength, and has very important significance for promoting the development of building energy-saving materials.
Description
Technical Field
The invention relates to the technical field of building materials, in particular to a water reducing agent suitable for high content of sandstone soil and a preparation method thereof.
Background
The cement concrete is an indispensable building material in the engineering bridge railways at present, and the concrete is usually prepared by mixing cement, sand, mineral fine powder, water and additives in a certain proportion. The development of the additive is benefited, so that various performances of the concrete are better and better, and the water reducing agent serving as an important additive is an absolute necessary condition for obtaining high-quality and high-performance concrete as a building material, and the development of the concrete technology and concept is further promoted. The water reducing agent is an additive which can reduce the water consumption required by the acceptable processability of concrete under the condition of ensuring that the concrete is easy to mix, or can improve the mixing property of the concrete and the strength of the concrete under the condition of keeping the unit water consumption unchanged. Therefore, the water reducing agent not only saves the water consumption in the concrete mixing and transporting process, but also can greatly improve the performance of the concrete in all aspects under the condition of low mixing amount.
However, in recent years, high-quality concrete raw materials are in short supply, sandstone resources are deteriorated, the content of soil is high, the polycarboxylic acid water reducing agent is very sensitive to soil, the soil mainly comprises clay minerals such as montmorillonite, illite, kaolinite and the like, and the influence of the montmorillonite on the soil is the greatest. The clay minerals are generally layered aluminosilicate structures, and the special structure determines that the clay is easy to adsorb limited water reducing agent and free water in slurry, so that the effective adsorption amount of cement particles is reduced, the dispersibility and dispersion retentivity of the polycarboxylic acid water reducing agent are reduced, the water reducing performance of the polycarboxylic acid water reducing agent is difficult to exert, the viscosity of a concrete mixture is too high, the slump retentivity is low, and the further application of the polycarboxylic acid water reducing agent in premixed concrete is greatly limited; on the other hand, the sand-stone mud content is too high, the normal water-cement ratio of the concrete mixture is influenced, the cohesiveness of the cement material is reduced, the mechanical property and the durability of the concrete mixture are seriously influenced, and more importantly, the adverse effect is caused on the service life of the building.
Based on the above situation, the water reducing agent suitable for high content of sandstone soil is developed, so that the polycarboxylate water reducing agent has good dispersibility and dispersion retentivity, can exert the water reducing performance of the water reducing agent, avoids overlarge viscosity of concrete mixture, low slump retentivity and low compressive strength, and has very important significance for promoting the development of building energy-saving materials.
Disclosure of Invention
The invention provides a water reducing agent suitable for high-content concrete, which has good dispersibility and dispersion retentivity, can exert the water reducing performance of a polycarboxylic acid water reducing agent, can avoid the problems of too high viscosity, low slump retentivity and low compressive strength influence on concrete mixtures, and has very important significance for promoting the development of building energy-saving materials.
In order to achieve the purpose, the invention adopts the technical scheme that: the water reducing agent suitable for high sand and soil content is characterized by comprising a corn xylitol maleic acid ester/isobutylene alcohol polyoxyethylene ether/acrylic acid copolymer which is formed by polymerizing isobutylene alcohol polyoxyethylene ether, corn xylitol maleic acid ester and acrylic acid serving as monomers.
Furthermore, the preparation method of the corn xylitol maleate/methacrylate polyoxyethylene ether/acrylic acid copolymer comprises the following steps:
step I, preparing corn xylitol maleate: respectively dissolving corn xylitol and maleic anhydride in N, N-dimethylformamide to obtain a corn xylitol solution and a maleic anhydride solution, uniformly mixing the corn xylitol solution and the maleic anhydride solution, reacting at 80-100 ℃ for 3-5h, cooling to room temperature, carrying out suction filtration, collecting filtrate, concentrating, adding 20% by mass of dilute hydrochloric acid to adjust the pH to 5, extracting with ethyl acetate, collecting an organic phase, and concentrating to obtain the corn xylitol maleic acid ester.
Step II, preparation of corn xylitol maleate/isobutylene polyoxyethylene ether/acrylic acid copolymer: dissolving acrylic acid and the corn xylitol maleic acid ester obtained in the step I in deionized water to obtain a solution A, dissolving the rongalite and mercaptopropionic acid in deionized water, uniformly mixing to obtain a solution B, dissolving the isobutylene alcohol polyoxyethylene ether in deionized water, adding hydrogen peroxide and ferrous sulfate, stirring for 10-30min, slowly adding the solution A and the solution B, wherein the adding time of the solution A is 2.5-3.5h, the adding time of the solution B is 3-4h, and reacting for 2-4h to obtain the corn xylitol maleic acid ester/isobutylene alcohol polyoxyethylene ether/acrylic acid copolymer.
Furthermore, the molar ratio of the corn xylitol to the maleic anhydride in the step I is (1-1.2): 1.
Furthermore, the molar ratio of the isobutylene alcohol polyoxyethylene ether, the corn xylitol maleic acid ester and the acrylic acid in the step II is 1 (0.6-1) to 3-5.
Furthermore, the concrete water reducing agent suitable for high-content sandstone soil also comprises 4-bromomethyl benzyl alcohol/triethylamine/phosphoric acid, and the mass of the 4-bromomethyl benzyl alcohol/triethylamine/phosphoric acid is 4-6% of the mass of the corn xylitol maleic acid ester/methacryloyl alcohol polyoxyethylene ether/acrylic acid copolymer.
Further, the mass of the 4-bromomethylbenzyl alcohol/triethylamine/phosphoric acid is preferably 5% of that of the corn xylitol maleate/methacryloxypolyoxyethylene ether/acrylic acid copolymer.
Further, the preparation method of the 4-bromomethylbenzyl alcohol/triethylamine/phosphoric acid comprises the following steps:
step I, preparation of 4-bromomethylbenzyl alcohol/triethylamine: adding 4-bromomethylbenzyl alcohol and triethylamine into absolute ethyl alcohol, carrying out reflux reaction for 5-9h at 70-80 ℃, cooling to room temperature, concentrating, adding ethyl acetate and acetone solution, carrying out suction filtration, and collecting a filter cake to obtain 4-bromomethylbenzyl alcohol/triethylamine;
step II, preparation of 4-bromomethylbenzyl alcohol/triethylamine/phosphoric acid: adding the 4-bromomethyl benzyl alcohol/triethylamine obtained in the step I into a reaction kettle, adding phosphorus pentoxide while stirring at 40-50 ℃, heating to 60-80 ℃, reacting for 2-4h, adding deionized water, reacting for 1-3h, adding 1-3mol/L sodium bicarbonate solution until the pH value is 7-8, standing and separating a lower layer to obtain the 4-bromomethyl benzyl alcohol/triethylamine/phosphoric acid.
Furthermore, in the step I, the molar ratio of the 4-bromomethylbenzyl alcohol to the triethylamine is 1 (1-1.2), and the volume ratio of the ethyl acetate to the acetone is (1-3): 1.
Furthermore, the mol ratio of the 4-bromomethylbenzyl alcohol/triethylamine, the phosphorus pentoxide and the deionized water in the step II is 2 (1-1.2) to (1-2).
Furthermore, the preparation method of the concrete water reducer suitable for high content of sandstone soil comprises the following steps: adding poly-4-bromomethylbenzyl alcohol/triethylamine/phosphoric acid and corn xylitol maleic acid ester/methacrylate polyoxyethylene ether/acrylic acid copolymer into deionized water, uniformly mixing, adding 30-50% by mass of sodium hydroxide to adjust the pH value to 6-7, and finally supplementing water to adjust the solid content to 40% to obtain the concrete water reducer with high sand and soil content.
Another object of the invention is to protect a concrete containing a water reducing agent suitable for high sand and soil content.
The beneficial effects of the invention are shown in the following aspects:
1. the corn xylitol is xylitol obtained by acid hydrolysis and hydrogenation of corncobs, the corn xylitol maleic acid ester is an esterified product of corn xylitol and maleic anhydride, the esterified product has a large amount of hydroxyl, the hydroxyl has strong hydrophilicity as a polar group, can adsorb free water, and forms a free water film on the surface of cement particles, and the free water film plays a role in lubricating and moisturizing the surface of the cement particles, so that the mutually flocculated cement particles are damaged, and the dispersibility of the cement is improved; the anionic carboxylic acid groups on the side chains of the traditional polycarboxylic acid water reducing agent are subjected to complex reaction with metal ions in cement slurry to inhibit the production of hydration products, the concentration of carboxylate ions in the slurry is reduced along with the passage of time, and the dispersion performance is lowered; the corn xylitol maleic acid ester and the phenyl on the 4-bromomethyl benzyl alcohol/triethylamine/phosphoric acid have larger steric hindrance, can be adsorbed on the surface of the clay, form a layer of hydrophobic protective film on the surface of the clay, reduce the adsorption of the clay to free water of a system, ensure that the clay cannot absorb water and swell, and cannot reduce the dispersibility of cement.
2. The cement has good dispersibility, so that the cement is fully contacted with the mixture, the premixed concrete has fewer bubbles, and the density of a cementing product is higher, so that the strength of the concrete can be greatly improved; the method can also ensure that sufficient space is provided for the growth of the ettringite, so that a space-type ettringite system is formed, the hydration reaction of the cement is increased while the dispersion performance of the corn xylitol maleic acid ester is improved, a large amount of calcium silicate (C-S-H gel) and flaky calcium hydroxide are generated, needle-shaped ettringite, calcium silicate, calcium hydroxide and other hydration products are mutually interpenetrated and lapped, the compressive strength of the cement stone is enhanced, and the problem of insufficient later strength of the concrete is solved.
3. 4-Bromomethylbenzyl alcohol/triethylamine/phosphoric acid has quaternary ammonium salt and phosphate radical, quaternary ammonium salt cation, and cation Na between clay layers+、K+、Ca2+Exchange occurs, and the water reducer is strongly adsorbed on the surface of soil through the acting forces of electrostatic attraction, hydrogen bonds, intermolecular and the like or is not easy to fall off between layers, so that the adsorption of the soil on the corn xylitol maleate/methacrylate polyoxyethylene ether/acrylic acid copolymer is reduced, the polycarboxylic acid water reducer is dispersed on the surface of cement particles, and the reduction of the slurry fluidity of cement is avoided; the sandstone with high soil content has high-content sulfate ions, the sulfate ions can be adsorbed to the surface of cement to influence the cementing reaction, and the phosphate ions can be preferentially adsorbed to the surface of the cement, so that the adsorption of the sulfate ions to the surface of the cement is reduced, and the concrete has good viscosity.
4. When the mass of the 4-bromomethyl benzyl alcohol/triethylamine/phosphoric acid is 5 percent of that of the corn xylitol maleic acid ester/isobutylene alcohol polyoxyethylene ether/acrylic acid copolymer, the maximum synergistic effect is generated, and the water reducing agent has good dispersibility and dispersion retentivity, so that the water reducing agent can exert the water reducing performance, a better mud resistant effect is achieved, the concrete mixture is prevented from having too high viscosity, low slump retentivity and low compressive strength, and the water reducing agent has good adaptability to high-content mud gravels.
Detailed Description
In order to make the technical solutions of the present invention better understood and make the above features, objects, and advantages of the present invention more comprehensible, the present invention is further described with reference to the following examples. The examples are intended to illustrate the invention only and are not intended to limit the scope of the invention.
The raw materials used in the following examples of the present invention were all purchased commercially.
Example 1
The water reducing agent suitable for high sand and soil content is characterized by comprising a corn xylitol maleic acid ester/isobutylene alcohol polyoxyethylene ether/acrylic acid copolymer which is formed by polymerizing isobutylene alcohol polyoxyethylene ether, corn xylitol maleic acid ester and acrylic acid serving as monomers.
Furthermore, the preparation method of the corn xylitol maleate/methacrylate polyoxyethylene ether/acrylic acid copolymer comprises the following steps:
step I, preparing corn xylitol maleate: respectively dissolving corn xylitol and maleic anhydride in N, N-dimethylformamide to obtain a corn xylitol solution and a maleic anhydride solution, uniformly mixing the corn xylitol solution and the maleic anhydride solution, reacting for 3 hours at 80 ℃, cooling to room temperature, carrying out suction filtration, collecting filtrate, concentrating, adding 20% by mass of dilute hydrochloric acid to adjust the pH to 5, extracting with ethyl acetate, collecting an organic phase, and concentrating to obtain the corn xylitol maleic acid ester.
Step II, preparation of corn xylitol maleate/isobutylene polyoxyethylene ether/acrylic acid copolymer: dissolving acrylic acid and the corn xylitol maleic acid ester obtained in the step I in deionized water to obtain a solution A, dissolving the rongalite and mercaptopropionic acid in deionized water, uniformly mixing to obtain a solution B, dissolving the isobutylene alcohol polyoxyethylene ether in deionized water, adding hydrogen peroxide and ferrous sulfate, stirring for 10min, slowly adding the solution A and the solution B, wherein the adding time of the solution A is 2.5h, the adding time of the solution B is 3h, and reacting for 2h to obtain the corn xylitol maleic acid ester/isobutylene alcohol polyoxyethylene ether/acrylic acid copolymer.
Further, the molar ratio of the corn xylitol to the maleic anhydride in the step I is 1:1.
Further, the molar ratio of the polyoxyethylene methacrylate, the corn xylitol maleate and the acrylic acid in the step II is 1:0.6: 3.
Furthermore, the concrete water reducing agent suitable for high-content sandstone soil also comprises 4-bromomethyl benzyl alcohol/triethylamine/phosphoric acid, and the mass of the 4-bromomethyl benzyl alcohol/triethylamine/phosphoric acid is 4% of that of the corn xylitol maleate/methacryloxypolyoxyethylene ether/acrylic acid copolymer.
Further, the preparation method of the 4-bromomethylbenzyl alcohol/triethylamine/phosphoric acid comprises the following steps:
step I, preparation of 4-bromomethylbenzyl alcohol/triethylamine: adding 4-bromomethylbenzyl alcohol and triethylamine into absolute ethyl alcohol, carrying out reflux reaction for 5 hours at 70 ℃, cooling to room temperature, concentrating, adding ethyl acetate and acetone solution, carrying out suction filtration, and collecting a filter cake to obtain 4-bromomethylbenzyl alcohol/triethylamine;
step II, preparation of 4-bromomethylbenzyl alcohol/triethylamine/phosphoric acid: adding the 4-bromomethyl benzyl alcohol/triethylamine obtained in the step I into a reaction kettle, adding phosphorus pentoxide while stirring at 40 ℃, heating to 60 ℃, reacting for 2 hours, adding deionized water, reacting for 1 hour, adding 1mol/L sodium bicarbonate solution until the pH value is 7, standing and separating a lower layer to obtain the 4-bromomethyl benzyl alcohol/triethylamine/phosphoric acid.
Furthermore, in the step I, the molar ratio of the 4-bromomethylbenzyl alcohol to the triethylamine is 1:1, and the volume ratio of the ethyl acetate to the acetone is 1:1.
Further, the molar ratio of 4-bromomethylbenzyl alcohol/triethylamine, phosphorus pentoxide and deionized water in step II is 2:1: 1.
Furthermore, the preparation method of the concrete water reducer suitable for high content of sandstone soil comprises the following steps: adding poly-4-bromomethylbenzyl alcohol/triethylamine/phosphoric acid and corn xylitol maleic acid ester/methacrylate polyoxyethylene ether/acrylic acid copolymer into deionized water, uniformly mixing, adding 30% by mass of sodium hydroxide to adjust the pH value to 6, and finally supplementing water to adjust the solid content to 40% to obtain the concrete water reducer with high sandstone soil content.
Example 2
The water reducing agent suitable for high sand and soil content is characterized by comprising a corn xylitol maleic acid ester/isobutylene alcohol polyoxyethylene ether/acrylic acid copolymer which is formed by polymerizing isobutylene alcohol polyoxyethylene ether, corn xylitol maleic acid ester and acrylic acid serving as monomers.
Furthermore, the preparation method of the corn xylitol maleate/methacrylate polyoxyethylene ether/acrylic acid copolymer comprises the following steps:
step I, preparing corn xylitol maleate: respectively dissolving corn xylitol and maleic anhydride in N, N-dimethylformamide to obtain a corn xylitol solution and a maleic anhydride solution, uniformly mixing the corn xylitol solution and the maleic anhydride solution, reacting at 85 ℃ for 3.5h, cooling to room temperature, carrying out suction filtration, collecting filtrate, concentrating, adding 20% by mass of dilute hydrochloric acid to adjust the pH to 5, extracting with ethyl acetate, collecting an organic phase, and concentrating to obtain the corn xylitol maleic acid ester.
Step II, preparation of corn xylitol maleate/isobutylene polyoxyethylene ether/acrylic acid copolymer: dissolving acrylic acid and the corn xylitol maleic acid ester obtained in the step I in deionized water to obtain a solution A, dissolving the rongalite and mercaptopropionic acid in deionized water, uniformly mixing to obtain a solution B, dissolving the isobutylene alcohol polyoxyethylene ether in the deionized water, adding hydrogen peroxide and ferrous sulfate, stirring for 15min, slowly adding the solution A and the solution B, wherein the adding time of the solution A is 2.8h, the adding time of the solution B is 3.3h, and reacting for 2.5h to obtain the corn xylitol maleic acid ester/isobutylene alcohol polyoxyethylene ether/acrylic acid copolymer.
Further, the molar ratio of the corn xylitol to the maleic anhydride in the step I is 1.05:1.
Further, the molar ratio of the polyoxyethylene methacrylate, the corn xylitol maleate and the acrylic acid in the step II is 1:0.7: 3.5.
Furthermore, the concrete water reducing agent suitable for high-content sandstone soil also comprises 4-bromomethyl benzyl alcohol/triethylamine/phosphoric acid, and the mass of the 4-bromomethyl benzyl alcohol/triethylamine/phosphoric acid is 4.5 percent of the mass of the corn xylitol maleic acid ester/methacryloyl alcohol polyoxyethylene ether/acrylic acid copolymer.
Further, the preparation method of the 4-bromomethylbenzyl alcohol/triethylamine/phosphoric acid comprises the following steps:
step I, preparation of 4-bromomethylbenzyl alcohol/triethylamine: adding 4-bromomethylbenzyl alcohol and triethylamine into absolute ethyl alcohol, carrying out reflux reaction for 6 hours at 73 ℃, cooling to room temperature, concentrating, adding ethyl acetate and acetone solution, carrying out suction filtration, and collecting a filter cake to obtain 4-bromomethylbenzyl alcohol/triethylamine;
step II, preparation of 4-bromomethylbenzyl alcohol/triethylamine/phosphoric acid: adding the 4-bromomethyl benzyl alcohol/triethylamine obtained in the step I into a reaction kettle, adding phosphorus pentoxide while stirring at 43 ℃, heating to 65 ℃, reacting for 2.5 hours, adding deionized water, reacting for 1.5 hours, adding 1.5mol/L sodium bicarbonate solution until the pH value is 7.3, standing and separating a lower layer to obtain the 4-bromomethyl benzyl alcohol/triethylamine/phosphoric acid.
Furthermore, in the step I, the molar ratio of the 4-bromomethylbenzyl alcohol to the triethylamine is 1:1.05, and the volume ratio of the ethyl acetate to the acetone is 1.5: 1.
Further, the molar ratio of 4-bromomethylbenzyl alcohol/triethylamine, phosphorus pentoxide and deionized water in step II is 2:1.05: 1.05.
Furthermore, the preparation method of the concrete water reducer suitable for high content of sandstone soil comprises the following steps: adding poly-4-bromomethylbenzyl alcohol/triethylamine/phosphoric acid and corn xylitol maleic acid ester/methacrylate polyoxyethylene ether/acrylic acid copolymer into deionized water, uniformly mixing, adding 35% by mass of sodium hydroxide to adjust the pH value to 6.3, and finally supplementing water to adjust the solid content to 40% to obtain the concrete water reducer suitable for high sand and soil content.
Example 3
The water reducing agent suitable for high sand and soil content is characterized by comprising a corn xylitol maleic acid ester/isobutylene alcohol polyoxyethylene ether/acrylic acid copolymer which is formed by polymerizing isobutylene alcohol polyoxyethylene ether, corn xylitol maleic acid ester and acrylic acid serving as monomers.
Furthermore, the preparation method of the corn xylitol maleate/methacrylate polyoxyethylene ether/acrylic acid copolymer comprises the following steps:
step I, preparing corn xylitol maleate: respectively dissolving corn xylitol and maleic anhydride in N, N-dimethylformamide to obtain a corn xylitol solution and a maleic anhydride solution, uniformly mixing the corn xylitol solution and the maleic anhydride solution, reacting for 4 hours at 90 ℃, cooling to room temperature, carrying out suction filtration, collecting filtrate, concentrating, adding 20% by mass of dilute hydrochloric acid to adjust the pH to 5, extracting with ethyl acetate, collecting an organic phase, and concentrating to obtain the corn xylitol maleic acid ester.
Step II, preparation of corn xylitol maleate/isobutylene polyoxyethylene ether/acrylic acid copolymer: dissolving acrylic acid and the corn xylitol maleic acid ester obtained in the step I in deionized water to obtain a solution A, dissolving the rongalite and mercaptopropionic acid in deionized water, uniformly mixing to obtain a solution B, dissolving the isobutylene alcohol polyoxyethylene ether in deionized water, adding hydrogen peroxide and ferrous sulfate, stirring for 20min, slowly adding the solution A and the solution B, wherein the adding time of the solution A is 3 hours, the adding time of the solution B is 3.5 hours, and reacting for 3 hours to obtain the corn xylitol maleic acid ester/isobutylene alcohol polyoxyethylene ether/acrylic acid copolymer.
Further, the molar ratio of the corn xylitol to the maleic anhydride in the step I is 1.1:1.
Further, the molar ratio of the polyoxyethylene methacrylate, the corn xylitol maleate and the acrylic acid in the step II is 1:0.8: 4.
Furthermore, the concrete water reducing agent suitable for high-content sandstone soil also comprises 4-bromomethyl benzyl alcohol/triethylamine/phosphoric acid, and the mass of the 4-bromomethyl benzyl alcohol/triethylamine/phosphoric acid is 5% of the mass of the corn xylitol maleate/methacryloxypolyoxyethylene ether/acrylic acid copolymer.
Further, the preparation method of the 4-bromomethylbenzyl alcohol/triethylamine/phosphoric acid comprises the following steps:
step I, preparation of 4-bromomethylbenzyl alcohol/triethylamine: adding 4-bromomethylbenzyl alcohol and triethylamine into absolute ethyl alcohol, carrying out reflux reaction for 7 hours at 75 ℃, cooling to room temperature, concentrating, adding ethyl acetate and acetone solution, carrying out suction filtration, and collecting a filter cake to obtain 4-bromomethylbenzyl alcohol/triethylamine;
step II, preparation of 4-bromomethylbenzyl alcohol/triethylamine/phosphoric acid: adding the 4-bromomethyl benzyl alcohol/triethylamine obtained in the step I into a reaction kettle, adding phosphorus pentoxide while stirring at 45 ℃, heating to 70 ℃, reacting for 3 hours, adding deionized water, reacting for 2 hours, adding 2mol/L sodium bicarbonate solution until the pH value is 7.5, and standing to separate out a lower layer to obtain the 4-bromomethyl benzyl alcohol/triethylamine/phosphoric acid.
Furthermore, in the step I, the molar ratio of the 4-bromomethylbenzyl alcohol to the triethylamine is 1:1.1, and the volume ratio of the ethyl acetate to the acetone is 2:1.
Further, the molar ratio of 4-bromomethylbenzyl alcohol/triethylamine, phosphorus pentoxide and deionized water in step II is 2:1.1: 1.5.
Furthermore, the preparation method of the concrete water reducer suitable for high content of sandstone soil comprises the following steps: adding poly-4-bromomethylbenzyl alcohol/triethylamine/phosphoric acid and corn xylitol maleic acid ester/methacrylate polyoxyethylene ether/acrylic acid copolymer into deionized water, uniformly mixing, adding 40% by mass of sodium hydroxide to adjust the pH value to 6.5, and finally supplementing water to adjust the solid content to 40% to obtain the concrete water reducer suitable for high sand and soil content.
Example 4
The water reducing agent suitable for high sand and soil content is characterized by comprising a corn xylitol maleic acid ester/isobutylene alcohol polyoxyethylene ether/acrylic acid copolymer which is formed by polymerizing isobutylene alcohol polyoxyethylene ether, corn xylitol maleic acid ester and acrylic acid serving as monomers.
Furthermore, the preparation method of the corn xylitol maleate/methacrylate polyoxyethylene ether/acrylic acid copolymer comprises the following steps:
step I, preparing corn xylitol maleate: respectively dissolving corn xylitol and maleic anhydride in N, N-dimethylformamide to obtain a corn xylitol solution and a maleic anhydride solution, uniformly mixing the corn xylitol solution and the maleic anhydride solution, reacting for 4.5 hours at 95 ℃, cooling to room temperature, carrying out suction filtration, collecting filtrate, concentrating, adding 20 mass percent of dilute hydrochloric acid to adjust the pH to 5, extracting by using ethyl acetate, collecting an organic phase, and concentrating to obtain the corn xylitol maleic acid ester.
Step II, preparation of corn xylitol maleate/isobutylene polyoxyethylene ether/acrylic acid copolymer: dissolving acrylic acid and the corn xylitol maleic acid ester obtained in the step I in deionized water to obtain a solution A, dissolving the rongalite and mercaptopropionic acid in deionized water, uniformly mixing to obtain a solution B, dissolving the isobutylene alcohol polyoxyethylene ether in deionized water, adding hydrogen peroxide and ferrous sulfate, stirring for 25min, slowly adding the solution A and the solution B, wherein the adding time of the solution A is 3.3h, the adding time of the solution B is 3.8h, and reacting for 3.5h to obtain the corn xylitol maleic acid ester/isobutylene alcohol polyoxyethylene ether/acrylic acid copolymer.
Further, the molar ratio of corn xylitol to maleic anhydride in step I is 1.15:1.
Further, the molar ratio of the polyoxyethylene methacrylate, the corn xylitol maleate and the acrylic acid in the step II is 1:0.9: 4.5.
Furthermore, the concrete water reducing agent suitable for high-content sandstone soil also comprises 4-bromomethyl benzyl alcohol/triethylamine/phosphoric acid.
Furthermore, the concrete water reducing agent suitable for high-content sandstone soil also comprises 4-bromomethyl benzyl alcohol/triethylamine/phosphoric acid, and the mass of the 4-bromomethyl benzyl alcohol/triethylamine/phosphoric acid is 5.5% of that of the corn xylitol maleate/methacryloxypolyethylene ether/acrylic acid copolymer.
Further, the preparation method of the 4-bromomethylbenzyl alcohol/triethylamine/phosphoric acid comprises the following steps:
step I, preparation of 4-bromomethylbenzyl alcohol/triethylamine: adding 4-bromomethylbenzyl alcohol and triethylamine into absolute ethyl alcohol, carrying out reflux reaction for 8 hours at 78 ℃, cooling to room temperature, concentrating, adding ethyl acetate and acetone solution, carrying out suction filtration, and collecting a filter cake to obtain 4-bromomethylbenzyl alcohol/triethylamine;
step II, preparation of 4-bromomethylbenzyl alcohol/triethylamine/phosphoric acid: adding the 4-bromomethyl benzyl alcohol/triethylamine obtained in the step I into a reaction kettle, adding phosphorus pentoxide while stirring at 48 ℃, heating to 75 ℃, reacting for 3.5 hours, adding deionized water, reacting for 2.5 hours, adding 2.5mol/L sodium bicarbonate solution until the pH value is 7.8, standing and separating a lower layer to obtain the 4-bromomethyl benzyl alcohol/triethylamine/phosphoric acid.
Furthermore, in the step I, the molar ratio of the 4-bromomethylbenzyl alcohol to the triethylamine is 1:1.15, and the volume ratio of the ethyl acetate to the acetone is 2.5: 1. ' Qiyi
Further, the molar ratio of 4-bromomethylbenzyl alcohol/triethylamine, phosphorus pentoxide and deionized water in step II is 2:1.15: 1.8.
Furthermore, the preparation method of the concrete water reducer suitable for high content of sandstone soil comprises the following steps: adding poly-4-bromomethylbenzyl alcohol/triethylamine/phosphoric acid and corn xylitol maleic acid ester/methacrylate polyoxyethylene ether/acrylic acid copolymer into deionized water, uniformly mixing, adding 45 mass percent of sodium hydroxide to adjust the pH value to 6.8, and finally supplementing water to adjust the solid content to 40% to obtain the concrete water reducer with high sandstone soil content.
Example 5
The water reducing agent suitable for high sand and soil content is characterized by comprising a corn xylitol maleic acid ester/isobutylene alcohol polyoxyethylene ether/acrylic acid copolymer which is formed by polymerizing isobutylene alcohol polyoxyethylene ether, corn xylitol maleic acid ester and acrylic acid serving as monomers.
Furthermore, the preparation method of the corn xylitol maleate/methacrylate polyoxyethylene ether/acrylic acid copolymer comprises the following steps:
step I, preparing corn xylitol maleate: respectively dissolving corn xylitol and maleic anhydride in N, N-dimethylformamide to obtain a corn xylitol solution and a maleic anhydride solution, uniformly mixing the corn xylitol solution and the maleic anhydride solution, reacting for 5 hours at 100 ℃, cooling to room temperature, carrying out suction filtration, collecting filtrate, concentrating, adding 20% by mass of dilute hydrochloric acid to adjust the pH to 5, extracting with ethyl acetate, collecting an organic phase, and concentrating to obtain the corn xylitol maleic acid ester.
Step II, preparation of corn xylitol maleate/isobutylene polyoxyethylene ether/acrylic acid copolymer: dissolving acrylic acid and the corn xylitol maleic acid ester obtained in the step I in deionized water to obtain a solution A, dissolving the rongalite and mercaptopropionic acid in deionized water, uniformly mixing to obtain a solution B, dissolving the isobutylene alcohol polyoxyethylene ether in deionized water, adding hydrogen peroxide and ferrous sulfate, stirring for 30min, slowly adding the solution A and the solution B, wherein the adding time of the solution A is 3.5h, the adding time of the solution B is 4h, and reacting for 4h to obtain the corn xylitol maleic acid ester/isobutylene alcohol polyoxyethylene ether/acrylic acid copolymer.
Further, the molar ratio of the corn xylitol to the maleic anhydride in the step I is 1.2: 1.
Furthermore, the molar ratio of the polyoxyethylene methacrylate, the corn xylitol maleic acid ester and the acrylic acid in the step II is 1:1: 5.
Furthermore, the concrete water reducing agent suitable for high-content sandstone soil also comprises 4-bromomethyl benzyl alcohol/triethylamine/phosphoric acid.
Furthermore, the concrete water reducing agent suitable for high-content sandstone soil also comprises 4-bromomethyl benzyl alcohol/triethylamine/phosphoric acid, and the mass of the 4-bromomethyl benzyl alcohol/triethylamine/phosphoric acid is 6% of the mass of the corn xylitol maleate/methacryloxypolyoxyethylene ether/acrylic acid copolymer.
Further, the preparation method of the 4-bromomethylbenzyl alcohol/triethylamine/phosphoric acid comprises the following steps:
step I, preparation of 4-bromomethylbenzyl alcohol/triethylamine: adding 4-bromomethylbenzyl alcohol and triethylamine into absolute ethyl alcohol, carrying out reflux reaction at 80 ℃ for 9 hours, cooling to room temperature, concentrating, adding ethyl acetate and acetone solution, carrying out suction filtration, and collecting a filter cake to obtain 4-bromomethylbenzyl alcohol/triethylamine;
step II, preparation of 4-bromomethylbenzyl alcohol/triethylamine/phosphoric acid: adding the 4-bromomethyl benzyl alcohol/triethylamine obtained in the step I into a reaction kettle, adding phosphorus pentoxide while stirring at 50 ℃, heating to 80 ℃, reacting for 4 hours, adding deionized water, reacting for 3 hours, adding 3mol/L sodium bicarbonate solution until the pH value is 8, standing and separating a lower layer to obtain the 4-bromomethyl benzyl alcohol/triethylamine/phosphoric acid.
Furthermore, in the step I, the molar ratio of the 4-bromomethylbenzyl alcohol to the triethylamine is 1:1.2, and the volume ratio of the ethyl acetate to the acetone is 3: 1.
Further, the molar ratio of 4-bromomethylbenzyl alcohol/triethylamine, phosphorus pentoxide and deionized water in step II is 2:1.2: 2.
Furthermore, the preparation method of the concrete water reducer suitable for high content of sandstone soil comprises the following steps: adding poly-4-bromomethylbenzyl alcohol/triethylamine/phosphoric acid and corn xylitol maleic acid ester/methacrylate polyoxyethylene ether/acrylic acid copolymer into deionized water, uniformly mixing, adding 50% by mass of sodium hydroxide to adjust the pH value to 7, and finally supplementing water to adjust the solid content to 40% to obtain the concrete water reducer with high sand and soil content.
Comparative example 1
A water reducing agent suitable for high content of sandstone soil is basically the same as the water reducing agent in the example 1 in preparation method and formula, and the difference is only: no corn xylitol maleate/polyoxyethylene methacrylate/acrylic acid copolymer was added.
Comparative example 2
A water reducing agent suitable for high content of sandstone soil is basically the same as the water reducing agent in the example 1 in preparation method and formula, and the difference is only: no 4-bromomethylbenzyl alcohol/triethylamine/phosphoric acid was added.
Comparative example 3
A water reducing agent suitable for high content of sandstone soil is basically the same as the water reducing agent in the example 1 in preparation method and formula, and the difference is only: instead of the corn xylitol maleate/polyoxyethylene methacrylate/acrylic acid copolymer, a polyoxyethylene methacrylate/acrylic acid copolymer was used.
Comparative example 4
A water reducing agent suitable for high content of sandstone soil is basically the same as the water reducing agent in the example 1 in preparation method and formula, and the difference is only: 4-bromomethylbenzyl alcohol/triethylamine was used instead of 4-bromomethylbenzyl alcohol/triethylamine/phosphoric acid.
Comparative example 5
The common polycarboxylic acid water reducing agent is sold in the market.
The experimental results are as follows:
the cement prepared from the polycarboxylic acid water reducing agent of examples 1-5 and comparative examples 1-5 was doped with 3% of montmorillonite, and the test results of the determination of the fluidity, water reducing rate, slump and compressive strength of the cement paste are shown in Table 1.
TABLE 1 Cement produced by using water reducing agent in different examples, which is mixed with 3% montmorillonite, has fluidity, water reducing rate, slump constant and compressive strength for cement paste
As can be seen from Table 1, the cement prepared from the water reducer with high content of sandstone and soil, disclosed by the embodiment of the invention, is doped with 3% of montmorillonite, and compared with a common commercially available polycarboxylic acid water reducer, the cement paste has more excellent fluidity, water reduction rate, slump constant and compressive strength, and has good adaptability to sandstone with high content of soil.
The foregoing shows and describes the general principles, essential features, and advantages of the invention. It will be understood by those skilled in the art that the present invention is not limited to the embodiments described above, which are merely illustrative of the principles of the invention, but that various changes and modifications may be made without departing from the spirit and scope of the invention, which fall within the scope of the invention as claimed. The scope of the invention is defined by the appended claims and equivalents thereof.
Claims (10)
1. The water reducing agent suitable for high sand and soil content is characterized by comprising a corn xylitol maleic acid ester/isobutylene alcohol polyoxyethylene ether/acrylic acid copolymer which is formed by polymerizing isobutylene alcohol polyoxyethylene ether, corn xylitol maleic acid ester and acrylic acid serving as monomers.
2. The water reducing agent suitable for high content of sandstone soil according to claim 1, wherein the preparation method of the corn xylitol maleate/methacrylate polyoxyethylene ether/acrylic acid copolymer comprises the following steps:
step I, preparing corn xylitol maleate: respectively dissolving corn xylitol and maleic anhydride in N, N-dimethylformamide to obtain a corn xylitol solution and a maleic anhydride solution, uniformly mixing the corn xylitol solution and the maleic anhydride solution, reacting at 80-100 ℃ for 3-5h, cooling to room temperature, carrying out suction filtration, collecting filtrate, concentrating, adding 20% by mass of dilute hydrochloric acid to adjust the pH to 5, extracting with ethyl acetate, collecting an organic phase, and concentrating to obtain the corn xylitol maleic acid ester.
Step II, preparation of corn xylitol maleate/isobutylene polyoxyethylene ether/acrylic acid copolymer: dissolving acrylic acid and the corn xylitol maleic acid ester obtained in the step I in deionized water to obtain a solution A, dissolving the rongalite and mercaptopropionic acid in deionized water, uniformly mixing to obtain a solution B, dissolving the isobutylene alcohol polyoxyethylene ether in deionized water, adding hydrogen peroxide and ferrous sulfate, stirring for 10-30min, slowly adding the solution A and the solution B, wherein the adding time of the solution A is 2.5-3.5h, the adding time of the solution B is 3-4h, and reacting for 2-4h to obtain the corn xylitol maleic acid ester/isobutylene alcohol polyoxyethylene ether/acrylic acid copolymer.
3. The water reducing agent suitable for high content of sandstone soil according to claim 2, wherein the molar ratio of corn xylitol to maleic anhydride in step I is (1-1.2): 1.
4. The water reducing agent for high content of sandstone soil as claimed in claim 2, wherein the molar ratio of the isobutylene alcohol polyoxyethylene ether, the corn xylitol maleic acid ester and the acrylic acid in the step II is 1 (0.6-1) to (3-5).
5. The water reducing agent for high content of sandstone soil as claimed in claim 1, wherein the water reducing agent for high content of sandstone soil further comprises 4-bromomethyl benzyl alcohol/triethylamine/phosphoric acid, and the mass of the 4-bromomethyl benzyl alcohol/triethylamine/phosphoric acid is 4-6% of the mass of the corn xylitol maleate/methacryloxypolyoxyethylene ether/acrylic acid copolymer.
6. The water reducing agent suitable for high sandstone soil content according to claim 5, wherein the mass of the 4-bromomethylbenzyl alcohol/triethylamine/phosphoric acid is 5% of that of the corn xylitol maleate/methacryloxypolyoxyethylene ether/acrylic acid copolymer.
7. The water reducing agent suitable for high content of sandstone soil according to claim 6, wherein the preparation method of the 4-bromomethyl benzyl alcohol/triethylamine/phosphoric acid comprises the following steps:
step I, preparation of 4-bromomethylbenzyl alcohol/triethylamine: adding 4-bromomethylbenzyl alcohol and triethylamine into absolute ethyl alcohol, carrying out reflux reaction for 5-9h at 70-80 ℃, cooling to room temperature, concentrating, adding ethyl acetate and acetone solution, carrying out suction filtration, and collecting a filter cake to obtain 4-bromomethylbenzyl alcohol/triethylamine;
step II, preparation of 4-bromomethylbenzyl alcohol/triethylamine/phosphoric acid: adding the 4-bromomethyl benzyl alcohol/triethylamine obtained in the step I into a reaction kettle, adding phosphorus pentoxide while stirring at 40-50 ℃, heating to 60-80 ℃, reacting for 2-4h, adding deionized water, reacting for 1-3h, adding 1-3mol/L sodium bicarbonate solution until the pH value is 7-8, standing and separating a lower layer to obtain the 4-bromomethyl benzyl alcohol/triethylamine/phosphoric acid.
8. The water reducing agent suitable for high content of sandstone soil according to claim 7, wherein the molar ratio of 4-bromomethylbenzyl alcohol and triethylamine in the step I is 1 (1-1.2), and the volume ratio of ethyl acetate and acetone is (1-3) to 1.
9. The water reducing agent for high content of sand and soil as claimed in claim 7, wherein the molar ratio of 4-bromomethylbenzyl alcohol/triethylamine, phosphorus pentoxide and deionized water in step II is 2 (1-1.2) to (1-2).
10. The water reducer suitable for the concrete with high content of sandstone soil according to any one of claims 1 to 9, wherein the preparation method of the concrete water reducer suitable for the concrete with high content of sandstone soil comprises the following steps: adding poly-4-bromomethylbenzyl alcohol/triethylamine/phosphoric acid and corn xylitol maleic acid ester/methacrylate polyoxyethylene ether/acrylic acid copolymer into deionized water, uniformly mixing, adding 30-50% by mass of sodium hydroxide to adjust the pH value to 6-7, and finally supplementing water to adjust the solid content to 40% to obtain the concrete water reducer with high sand and soil content.
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