Functional polycarboxylate superplasticizer as well as preparation method and application thereof

Abstract

The invention provides a functional polycarboxylic acid water reducing agent as well as a preparation method and application thereof, and relates to the technical field of water reducing agents. The functional polycarboxylic acid water reducing agent provided by the invention comprises the polycarboxylic acid water reducing agent mother liquor, the thickening water-retaining agent and the air entraining agent, and the thickening water-retaining agent and the polycarboxylic acid water reducing agent have good solubility after being mixed, so that the rheological property of fresh concrete can be remarkably improved; compared with conventional carboxymethyl cellulose ether, hydroxy propyl cellulose ether, polyacrylamide and the like, the concrete provided by the invention has the advantages of good solubility, small sensitivity to materials, certain auxiliary dispersion effect and plastic retaining effect, and can solve the problem that during commercial concrete construction, due to various poor gradation, more mud powder or stone powder is contained in artificial aggregate or recycled aggregate, and the service life of the concrete is prolonged. The problems of poor bleeding and segregation phenomena of concrete, poor rheological property, poor freezing resistance, poor impermeability, poor slump gradual loss and the like caused by insufficient air entraining are solved.

Description

Technical Field

[0001] This application relates to the technical field of water reducers, and particularly relates to a functional polycarboxylate water reducer, its preparation method and application. Background Art

[0002] Polycarboxylate water reducers have the advantages of high water reduction rate, high slump retention and environmental friendliness, and are essential external additives for cement-based concrete, but they are relatively sensitive to the gradation, mud powder and stone powder content of aggregates. In recent years, with the rapid development of national infrastructure projects, high-quality sand and gravel resources have become increasingly scarce. In construction, artificial aggregates and recycled aggregates have to be used. Due to their poor gradation and high mud powder or stone powder content, it brings great problems to on-site construction, and at the same time affects the quality of fresh concrete and hardened concrete, posing great potential quality hazards to construction projects and seriously affecting the service life of building structures. Summary of the Invention

[0003] The purpose of this application is to provide a functional polycarboxylate water reducer, its preparation method and application, aiming to solve the problem that the existing artificial aggregates and recycled aggregates have poor gradation and high mud powder or stone powder content, thus affecting the quality of fresh concrete and hardened concrete.

[0004] To achieve the above purpose, this application provides a functional polycarboxylate water reducer, which includes, by mass parts: 180 - 220 parts of polycarboxylate water reducer mother liquor, 860 - 900 parts of water, 20 - 40 parts of thickening and water retaining agent, and 1 - 3 parts of air-entraining agent.

[0005] In some embodiments, the polycarboxylate water reducer mother liquor, the thickening and water retaining agent, and the air-entraining agent all include functional monomers;

[0006] The functional monomers include, by mass parts: 500 - 550 parts of hydroxyethyl acrylate, 165 - 185 parts of phosphoric acid, 1.0 - 1.8 parts of hydroquinone, and 1.0 - 1.8 parts of p-toluenesulfonic acid.

[0007] In some embodiments, the thickening and water retaining agent includes, by mass parts: 90 - 110 parts of methyl allyl polyoxyethylene ether, 10 - 30 parts of acrylic acid, 2 - 4 parts of ammonium persulfate, 0.2 - 0.3 parts of vitamin C, 0.5 - 0.7 parts of mercaptopropionic acid, 42 - 62 parts of acrylic acid, 0.2 - 0.4 parts of N-hydroxymethyl acrylamide, 0.2 - 0.4 parts of N,N-methylenebisacrylamide, 8 - 12 parts of functional monomers, and 700 - 780 parts of water.

[0008] In some embodiments, the air-entraining agent, by mass parts, comprises: 70-80 parts of a thickening and water-retaining agent, 15-20 parts of sodium lauryl polyoxyethylene ether sulfate, 6-12 parts of Tween 20, and 4-8 parts of coconut oil fatty acid diethanolamide.

[0009] In some embodiments, the polycarboxylate superplasticizer mother liquor, by mass parts, comprises: 0.1-0.4 parts of mercaptopropionic acid, 0.1-0.3 parts of mercaptoacetic acid, 0.2-0.6 parts of isopropyl alcohol, 0.3-0.5 parts of sodium isascorbate, 0.1-0.5 parts of vitamin C, 10-16 parts of acrylic acid, 1-4 parts of 2-acrylamido-2-methylpropanesulfonic acid, 1-4 parts of hydroxypropyl acrylate, 1-4 parts of sodium methallylsulfonate, 1-4 parts of a functional monomer, 40-60 parts of isopentenyl polyethylene glycol ether, 40-60 parts of methyl vinyl polyethylene glycol ether, 0.2-0.6 parts of hydrogen peroxide solution, 0.6-1.0 parts of azodicyanovaleric acid, 11-15 parts of sodium hydroxide solution, and 87-126 parts of water.

[0010] In some embodiments, the mass percentage concentration of the hydrogen peroxide solution is 27.5%, the mass percentage concentration of the sodium hydroxide solution is 32%, and the pH value of the polycarboxylate superplasticizer mother liquor is 5-8.

[0011] This application also provides a preparation method of the above functional polycarboxylate superplasticizer, comprising: separately preparing the polycarboxylate superplasticizer mother liquor, the thickening and water-retaining agent, and the air-entraining agent, and uniformly stirring the polycarboxylate superplasticizer mother liquor, the thickening and water-retaining agent, the air-entraining agent, and water to obtain the functional polycarboxylate superplasticizer.

[0012] In some embodiments, the preparation method of the thickening and water-retaining agent comprises:

[0013] Adding methallyl polyethylene glycol ether, 210-230 parts of water, acrylic acid, and ammonium persulfate into a reaction kettle as the bottom materials of the kettle; after the bottom materials of the kettle are stirred evenly, simultaneously dropping material A and material B; material A is a mixed solution composed of vitamin C, mercaptopropionic acid, and 50-70 parts of water; material B is a mixed solution composed of acrylic acid, N-hydroxymethyl acrylamide, N,N-methylenebisacrylamide, a functional monomer, and 40-60 parts of water; after dropping, adding 400-420 parts of water, and stirring the materials evenly to obtain the thickening and water-retaining agent;

[0014] The preparation method of the functional monomer comprises:

[0015] Adding hydroxyethyl acrylate into a reaction kettle, when the temperature of the materials rises to 30°C - 40°C, sequentially adding phosphoric acid, hydroquinone, and p-toluenesulfonic acid, continuing to heat up to 95°C and keeping the temperature, controlling the temperature during heat preservation at 95 ± 5°C, after 4 hours of heat preservation, waiting for the temperature to drop below 45°C to obtain the functional monomer.

[0016] In some embodiments, the preparation method of the air-entraining agent comprises:

[0017] Adding a thickening water retainer, sodium lauryl polyoxyethylene ether sulfate, Tween 20, and coconut oil fatty acid diethanolamide into a reaction kettle, and stirring the above materials evenly to obtain the air-entraining agent;

[0018] The preparation method of the polycarboxylate superplasticizer mother liquor comprises:

[0019] Stirring mercaptopropionic acid, mercaptoacetic acid, isopropyl alcohol, sodium isascorbate, vitamin C, and 25 - 40 parts of water evenly to prepare a dropping material A;

[0020] Stirring acrylic acid, 2-acrylamido-2-methylpropanesulfonic acid, hydroxypropyl acrylate, sodium methallylsulfonate, a functional monomer, and 2 - 6 parts of water evenly to prepare a dropping material B;

[0021] Adding 60 - 80 parts of water, isopentenyl polyoxyethylene ether, methyl vinyl polyoxyethylene ether, hydrogen peroxide, and azodicyanovaleric acid into a reaction kettle as the bottom material in the kettle. After the powder materials are dissolved completely, simultaneously dropwise add the dropping material A and the dropping material B. After the dropping is completed, add a sodium hydroxide solution to adjust the pH value to 5 - 8 to obtain the polycarboxylate superplasticizer mother liquor.

[0022] This application also provides an application of the functional polycarboxylate superplasticizer as described above in the preparation of concrete.

[0023] Compared with the prior art, the beneficial effects of this application include:

[0024] The functional polycarboxylate superplasticizer provided by this application includes a polycarboxylate superplasticizer mother liquor, a thickening water retainer, and an air-entraining agent. After the thickening water retainer is mixed with the polycarboxylate superplasticizer, it has good solubility, can significantly improve the rheology of fresh concrete, and has good solubility, low sensitivity to materials, and also has a certain auxiliary dispersion effect and plasticizing effect compared with conventional carboxymethyl cellulose ether, hydroxypropyl cellulose ether, polyacrylamide, etc. It can solve the problems of poor bleeding and segregation of concrete caused by various poor gradings, high mud powder or stone powder content in artificial aggregates or recycled aggregates, and the deterioration of rheology, frost resistance, impermeability, and slump loss over time caused by insufficient air entrainment. The functional polycarboxylate superplasticizer of this application makes the bleeding rate of fresh concrete not more than 30% in artificial aggregate or recycled aggregate concrete, the air content can be controlled in the range of 3.0% - 5.5%, the slump loss over time within 3 hours is not more than +80, and the strength freeze-thaw loss rate after 50 times is not more than 90%. Detailed Embodiments

[0025] As used herein, the terms:

[0026] "Prepared by..." is synonymous with "comprising". As used herein, the terms "comprising", "including", "having", "containing" or any other variation thereof are intended to cover non-exclusive inclusion. For example, a composition, step, method, article or apparatus that comprises the recited elements need not be limited to those elements, but may include other elements not expressly listed or elements inherent to such composition, step, method, article or apparatus.

[0027] The conjunctive "consisting of" excludes any unrecited element, step or component. If used in a claim, this phrase renders the claim closed, excluding materials other than those described, except for conventional impurities associated therewith. When the phrase "consisting of" appears in a clause within the body of a claim rather than immediately following the subject, it limits only the elements described in that clause; other elements are not excluded from the claim as a whole.

[0028] When an equivalent, concentration, or other value or parameter is expressed as a range, a preferred range, or a range defined by a series of upper preferred values and lower preferred values, it should be understood that all ranges formed by any pairing of any upper range limit or preferred value with any lower range limit or preferred value are specifically disclosed, whether or not the ranges are separately disclosed. For example, when the range "1 to 5" is disclosed, the described range should be interpreted as including the ranges "1 to 4", "1 to 3", "1 to 2", "1 to 2 and 4 to 5", "1 to 3 and 5", etc. When a numerical range is described herein, unless otherwise stated, the range is intended to include its end values and all integers and fractions within the range.

[0029] In these examples, unless otherwise specified, the parts and percentages are by mass.

[0030] "Parts by mass" refers to the basic measurement unit representing the mass ratio relationship of multiple components. 1 part can represent any unit mass, such as 1 g or 2.689 g, etc. If we say that the mass parts of component A is a parts and the mass parts of component B is b parts, it means the mass ratio of component A to component B is a:b. Or, it means the mass of component A is aK and the mass of component B is bK (K is any number representing a multiple factor). It should not be misunderstood that, different from the mass fraction, the sum of the mass parts of all components is not limited to 100 parts.

[0031] The present application provides a functional polycarboxylate water reducer, calculated by mass parts, comprising: 180 - 220 parts of polycarboxylate water reducer mother liquor, 860 - 900 parts of water, 20 - 40 parts of thickening and water retaining agent, and 1 - 3 parts of air entraining agent.

[0032] Among them, the mass fraction of the polycarboxylate water-reducing agent mother liquor can be, for example, 180 parts, 190 parts, 200 parts, 210 parts, 220 parts, or any value between 180 - 220 parts; the mass fraction of water can be, for example, 860 parts, 870 parts, 880 parts, 890 parts, 900 parts, or any value between 860 - 900 parts; the mass fraction of the thickening and water-retaining agent can be, for example, 20 parts, 25 parts, 30 parts, 35 parts, 40 parts, or any value between 20 - 40 parts; the mass fraction of the air-entraining agent can be, for example, 1 part, 1.5 parts, 2 parts, 2.5 parts, 3 parts, or any value between 1 - 3 parts.

[0033] When the functional polycarboxylate water-reducing agent of the present application is applied to concrete, it can solve the problems such as poor bleeding and segregation of commercial concrete during construction due to various gradation differences, high content of mud powder or stone powder in artificial aggregates or recycled aggregates, resulting in poor rheology, frost resistance, impermeability, and slump loss over time caused by insufficient air entrainment. The functional polycarboxylate water-reducing agent of the present application in artificial aggregate or recycled aggregate concrete makes the bleeding rate of fresh concrete not greater than 30%, the air content can be controlled in the range of 3.0% - 5.5%, the slump loss over time within 3 hours is not greater than +80, and the strength freeze-thaw loss rate within 50 times is not greater than 90%.

[0034] In some embodiments, the polycarboxylate water-reducing agent mother liquor, the thickening and water-retaining agent, and the air-entraining agent all include functional monomers;

[0035] The functional monomers, by mass fraction, include: 500 - 550 parts of hydroxyethyl acrylate, 165 - 185 parts of phosphoric acid, 1.0 - 1.8 parts of hydroquinone, and 1.0 - 1.8 parts of p-toluenesulfonic acid.

[0036] Among them, the mass fraction of hydroxyethyl acrylate can be, for example, 500 parts, 510 parts, 520 parts, 530 parts, 540 parts, 550 parts, or any value between 500 - 550 parts; the mass fraction of phosphoric acid can be, for example, 165 parts, 170 parts, 175 parts, 180 parts, 185 parts, or any value between 165 - 185 parts; the mass fraction of hydroquinone can be, for example, 1.0 part, 1.1 parts, 1.2 parts, 1.3 parts, 1.4 parts, 1.5 parts, 1.6 parts, 1.7 parts, 1.8 parts, or any value between 1.0 - 1.8; the mass fraction of p-toluenesulfonic acid can be, for example, 1.0 part, 1.1 parts, 1.2 parts, 1.3 parts, 1.4 parts, 1.5 parts, 1.6 parts, 1.7 parts, 1.8 parts, or any value between 1.0 - 1.8.

[0037] In some embodiments, the thickening water retention agent, by mass parts, comprises: 90 - 110 parts of methyl allyl polyoxyethylene ether, 10 - 30 parts of acrylic acid, 2 - 4 parts of ammonium persulfate, 0.2 - 0.3 parts of vitamin C, 0.5 - 0.7 parts of mercaptopropionic acid, 42 - 62 parts of acrylic acid, 0.2 - 0.4 parts of N - hydroxymethyl acrylamide, 0.2 - 0.4 parts of N,N - methylenebisacrylamide, 8 - 12 parts of functional monomer, and 700 - 780 parts of water.

[0038] Among them, the molecular weight of methyl allyl polyoxyethylene ether is 2400. The mass parts of methyl allyl polyoxyethylene ether can be, for example, 90 parts, 95 parts, 100 parts, 105 parts, 110 parts, or any value between 90 - 110 parts; the mass parts of acrylic acid can be, for example, 10 parts, 15 parts, 20 parts, 25 parts, 30 parts, or any value between 10 - 30 parts; the mass parts of ammonium persulfate can be, for example, 2 parts, 2.5 parts, 3 parts, 3.5 parts, 4 parts, or any value between 2 - 4 parts; the mass parts of vitamin C can be, for example, 0.2 parts, 0.21 parts, 0.22 parts, 0.25 parts, 0.26 parts, 0.28 parts, 0.3 parts, or any value between 0.2 - 0.3 parts; the mass parts of mercaptopropionic acid can be, for example, 0.5 parts, 0.55 parts, 0.6 parts, 0.65 parts, 0.7 parts, or any value between 0.5 - 0.7 parts; the mass parts of acrylic acid can be, for example, 42 parts, 45 parts, 48 parts, 50 parts, 55 parts, 58 parts, 60 parts, 62 parts, or any value between 42 - 62 parts; the mass parts of N - hydroxymethyl acrylamide can be, for example, 0.2 parts, 0.21 parts, 0.22 parts, 0.25 parts, 0.26 parts, 0.28 parts, 0.3 parts, 0.35 parts, 0.38 parts, 0.4 parts, or any value between 0.2 - 0.4 parts; the mass parts of N,N - methylenebisacrylamide can be, for example, 0.2 parts, 0.21 parts, 0.22 parts, 0.25 parts, 0.26 parts, 0.28 parts, 0.3 parts, 0.35 parts, 0.38 parts, 0.4 parts, or any value between 0.2 - 0.4 parts; the mass parts of functional monomer can be, for example, 8 parts, 9 parts, 10 parts, 11 parts, 12 parts, or any value between 8 - 12 parts; the mass parts of water can be, for example, 700 parts, 710 parts, 720 parts, 730 parts, 740 parts, 750 parts, 760 parts, 770 parts, 780 parts, or any value between 700 - 780 parts.

[0039] After being mixed with the polycarboxylate superplasticizer, the thickening water retention agent has good solubility, can significantly improve the rheology of fresh concrete, and has good solubility, low sensitivity to materials, and also has certain auxiliary dispersion and plasticizing effects compared with conventional carboxymethyl cellulose ether, hydroxypropyl cellulose ether, polyacrylamide, etc.

[0040] In some embodiments, the air-entraining agent, by mass parts, includes: 70-80 parts of a thickening and water-retaining agent, 15-20 parts of sodium lauryl polyoxyethylene ether sulfate, 6-12 parts of Tween 20, and 4-8 parts of coconut oil fatty acid diethanolamide.

[0041] Among them, the mass parts of the thickening and water-retaining agent can be, for example, 70 parts, 72 parts, 75 parts, 78 parts, 80 parts, or any value between 70-80 parts; the thickening and water-retaining agent, as the viscosity-adjusting component of the air-entraining agent, can significantly improve the foam stability of the air-entraining agent.

[0042] Among them, the mass parts of sodium lauryl polyoxyethylene ether sulfate can be, for example, 15 parts, 16 parts, 17 parts, 18 parts, 19 parts, 20 parts, or any value between 15-20 parts; the mass parts of Tween 20 can be, for example, 6 parts, 7 parts, 8 parts, 9 parts, 10 parts, 11 parts, 12 parts, or any value between 6-12 parts; sodium lauryl polyoxyethylene ether sulfate and Tween 20 are the foaming components of the air-entraining agent.

[0043] Among them, the mass parts of coconut oil fatty acid diethanolamide can be, for example, 4 parts, 5 parts, 6 parts, 7 parts, 8 parts, or any value between 4-8 parts. Coconut oil fatty acid diethanolamide, as the foam-stabilizing component of the air-entraining agent, further improves the foam stability of the air-entraining agent.

[0044] In some embodiments, the polycarboxylate superplasticizer mother liquor, by mass parts, includes: 0.1-0.4 parts of mercaptopropionic acid, 0.1-0.3 parts of mercaptoacetic acid, 0.2-0.6 parts of isopropanol, 0.3-0.5 parts of sodium erythorbate, 0.1-0.5 parts of vitamin C, 10-16 parts of acrylic acid, 1-4 parts of 2-acrylamido-2-methylpropanesulfonic acid, 1-4 parts of hydroxypropyl acrylate, 1-4 parts of sodium methallylsulfonate, 1-4 parts of a functional monomer, 40-60 parts of isopentenyl polyoxyethylene ether, 40-60 parts of methylenyl polyoxyethylene ether, 0.2-0.6 parts of hydrogen peroxide, 0.6-1.0 parts of azodicyanovaleric acid, 11-15 parts of sodium hydroxide solution, and 87-126 parts of water.

[0045] Among them, the mass fraction of mercaptopropionic acid can be, for example, 0.1 part, 0.2 parts, 0.3 parts, 0.4 parts or any value between 0.1 and 0.4 parts; the mass fraction of mercaptoacetic acid can be, for example, 0.1 part, 0.2 parts, 0.3 parts or any value between 0.1 and 0.3 parts; the mass fraction of isopropyl alcohol can be, for example, 0.1 part, 0.2 parts, 0.3 parts, 0.4 parts, 0.5 parts, 0.6 parts or any value between 0.1 and 0.6 parts; the mass fraction of sodium erythorbate can be, for example, 0.3 parts, 0.4 parts, 0.5 parts or any value between 0.3 and 0.5 parts; the mass fraction of vitamin C can be, for example, 0.1 part, 0.2 parts, 0.3 parts, 0.4 parts, 0.5 parts or any value between 0.1 and 0.5 parts; the mass fraction of acrylic acid can be, for example, 10 parts, 11 parts, 12 parts, 13 parts, 14 parts, 15 parts, 16 parts or any value between 10 and 16 parts; the mass fraction of 2-acrylamido-2-methylpropanesulfonic acid, hydroxypropyl acrylate, sodium methallylsulfonate, and functional monomer can be, for example, 1 part, 2 parts, 3 parts, 4 parts or any value between 1 and 4 parts; the mass fraction of isopentenyl polyoxyethylene ether and methyl vinyl polyoxyethylene ether can be, for example, 40 parts, 45 parts, 50 parts, 55 parts, 60 parts or any value between 40 and 60 parts; the mass fraction of hydrogen peroxide solution can be, for example, 0.2 parts, 0.3 parts, 0.4 parts, 0.5 parts, 0.6 parts or any value between 0.2 and 0.6 parts; the mass fraction of azodicyanovaleric acid can be, for example, 0.6 parts, 0.7 parts, 0.8 parts, 0.9 parts, 1.0 parts or any value between 0.6 and 1.0 parts; the mass fraction of sodium hydroxide solution can be, for example, 11 parts, 12 parts, 13 parts, 14 parts, 15 parts or any value between 11 and 15 parts; the mass fraction of water can be, for example, 87 parts, 90 parts, 95 parts, 100 parts, 105 parts, 110 parts, 115 parts, 120 parts, 126 parts or any value between 87 and 126 parts.

[0046] In some embodiments, the mass percentage concentration of the hydrogen peroxide solution is 27.5%, the mass percentage concentration of the sodium hydroxide solution is 32%, and the pH value of the polycarboxylate superplasticizer mother liquor is 5 to 8, for example, it can be 5, 6, 7, 8 or any value between 5 and 8.

[0047] This application also provides a preparation method of the above functional polycarboxylate superplasticizer, including: separately preparing a polycarboxylate superplasticizer mother liquor, a thickening and water-retaining agent, and an air-entraining agent, and uniformly stirring the polycarboxylate superplasticizer mother liquor, the thickening and water-retaining agent, the air-entraining agent and water to obtain the functional polycarboxylate superplasticizer.

[0048] In some embodiments, the preparation method of the thickening and water-retaining agent includes:

[0049] Add allyl polyoxyethylene ether, 210 - 230 parts of water, acrylic acid, and ammonium persulfate into the reaction kettle as the bottom materials of the kettle; after the bottom materials of the kettle are stirred evenly, add material A and material B dropwise simultaneously; Material A is a mixed solution composed of vitamin C, mercaptopropionic acid, and 50 - 70 parts of water; Material B is a mixed solution composed of acrylic acid, N - hydroxymethylacrylamide, N,N - methylenebisacrylamide, functional monomer, and 40 - 60 parts of water; after the dropwise addition is completed, add 400 - 420 parts of water, and stir the materials evenly to obtain the thickening water - retaining agent;

[0050] The preparation method of the functional monomer includes:

[0051] Add hydroxyethyl acrylate into the reaction kettle. When the temperature of the material rises to 30°C - 40°C, for example, it can be 30°C, 35°C, 40°C or any value between 30°C - 40°C, add phosphoric acid, hydroquinone, and p - toluenesulfonic acid in sequence, continue to heat up to 95°C and keep the temperature, control the temperature during heat preservation at 95 ± 5°C, after 4 hours of heat preservation, when the temperature drops below 45°C, the functional monomer is obtained.

[0052] In some embodiments, the preparation method of the air - entraining agent includes:

[0053] Add the thickening water - retaining agent, sodium lauryl polyoxyethylene ether sulfate, Tween 20, and coconut oil fatty acid diethanolamide into the reaction kettle, and stir the above - mentioned materials evenly to obtain the air - entraining agent;

[0054] The preparation method of the polycarboxylate superplasticizer mother liquor includes:

[0055] Stir mercaptopropionic acid, mercaptoacetic acid, isopropanol, sodium erythorbate, vitamin C, and 25 - 40 parts of water evenly to prepare the A dropping material;

[0056] Stir acrylic acid, 2 - acrylamido - 2 - methylpropanesulfonic acid, hydroxypropyl acrylate, sodium methallylsulfonate, functional monomer, and 2 - 6 parts of water evenly to prepare the B dropping material;

[0057] Add 60 - 80 parts of water, isopentenyl polyoxyethylene ether, methylene polyoxyethylene ether, hydrogen peroxide, and azodicyanovaleric acid into the reaction kettle as the bottom materials of the kettle. After the powder materials are dissolved, add the A dropping material and the B dropping material dropwise simultaneously. After the dropwise addition is completed, add sodium hydroxide solution to adjust the pH value to 5 - 8 to obtain the polycarboxylate superplasticizer mother liquor.

[0058] This application also provides an application of the functional polycarboxylate superplasticizer as described above in the preparation of concrete.

[0059] Among them, the added mass percentage of the functional polycarboxylate water reducer in the concrete can be 0.12% - 0.20%, for example, it can be 0.12%, 0.15%, 0.17%, 0.19%, 0.20% or any value between 0.12% - 0.20%.

[0060] The implementation solutions of the present application will be described in detail below in conjunction with specific embodiments. However, those skilled in the art will understand that the following embodiments are only used to illustrate the present application and should not be regarded as limiting the scope of the present application. For those not specified in the embodiments, they are carried out according to the conventional conditions or the conditions recommended by the manufacturer. For reagents or instruments not specified by the manufacturer, they are all conventional products that can be obtained through commercial purchase.

[0061] Example 1

[0062] Example 1 provides a functional polycarboxylate water reducer, and its preparation method includes:

[0063] I. Preparation of highly efficient thickening and water retaining agent

[0064] (1) Add 90 parts by mass of methallyl polyoxyethylene ether (molecular weight: 2400), 210 parts of water, 10 parts of acrylic acid, and 2 parts of ammonium persulfate to the reaction kettle as the bottom materials.

[0065] (2) After the bottom materials are stirred evenly, simultaneously add dropwise Material A and Material B; Material A is a mixed solution composed of 0.2 parts of vitamin C, 0.5 parts of mercaptopropionic acid, and 50 parts of water; Material B is a mixed solution composed of 42 parts of acrylic acid, 0.2 parts of N-hydroxymethylacrylamide, 0.2 parts of N,N-methylenebisacrylamide, 8 parts of self-made functional monomer, and 40 parts of water; Material B is added dropwise for 45 minutes, and Material A is added dropwise for 60 minutes.

[0066] (3) After adding dropwise Material A, continue to stir and react for 60 minutes.

[0067] (4) After adding 400 parts of dilution water, stir the materials evenly to obtain the highly efficient thickening and water retaining agent.

[0068] II. Preparation of self-made functional monomer

[0069] (1) Add 500 parts by mass of hydroxyethyl acrylate to the reaction kettle.

[0070] (2) Start stirring and simultaneously raise the temperature.

[0071] (3) When the temperature of the material rises to 30 °C, add 165 parts of phosphoric acid, 1.0 part of hydroquinone, and 1.0 part of p-toluenesulfonic acid in sequence, and continue to raise the temperature simultaneously.

[0072] (4) When the temperature rises to 95 °C, start heat preservation. The heat preservation temperature is controlled at 95 ± 5 °C, and the heat preservation is carried out for 4 hours.

[0073] (5) After the heat preservation is completed, when the temperature drops below 45 °C, the material can be discharged to obtain the functional monomer.

[0074] III. Preparation of high-performance air-entraining agent

[0075] (1) Add 70 parts by mass of the self-made high-efficiency thickening and water-retaining agent to the reaction kettle;

[0076] (2) Add 15 parts by mass of sodium lauryl polyoxyethylene ether and 6 parts by mass of Tween 20 to the reaction kettle;

[0077] (3) Add 4 parts by mass of coconut oil fatty acid diethanolamide to the reaction kettle;

[0078] Mix the above materials evenly by mechanical stirring to obtain the high-performance air-entraining agent.

[0079] IV. Preparation of polycarboxylate superplasticizer mother liquor

[0080] (1) Weigh 0.1 part of mercaptopropionic acid, 0.1 part of mercaptoacetic acid, 0.2 part of isopropanol, 0.3 part of sodium isascorbate, 0.1 part of vitamin C and 25 parts of water respectively, stir evenly and prepare the A dropping material for waiting to be used.

[0081] (2) Weigh 10 parts of acrylic acid, 1 part of 2-acrylamido-2-methylpropanesulfonic acid, 1 part of hydroxypropyl acrylate, 1 part of sodium methallylsulfonate and 1 part of the self-made functional monomer, 2 parts of water respectively, stir evenly and prepare the B dropping material for waiting to be used.

[0082] (3) At room temperature, add 60 parts of water, 40 parts of isopentenyl polyoxyethylene ether, 40 parts of methallyl polyoxyethylene ether, 0.2 part of hydrogen peroxide (mass percentage concentration 27.5%), 0.6 part of azodicyanovaleric acid to the reaction kettle as the bottom material of the kettle in turn. After all the powder materials are dissolved, simultaneously dropwise add the A dropping material and the B dropping material. The A dropping material is added dropwise for 3.0 hours; the B dropping material is added dropwise for 2.5 hours. After adding the A dropping material dropwise, continue to stir and react for 1.0 hour, then add 11 parts of sodium hydroxide solution with a mass percentage concentration of 32% for neutralization reaction, and control the pH value of the material at 5-8 to discharge the material.

[0083] V. Preparation of functional polycarboxylate superplasticizer

[0084] (1) Add 180 parts by mass of the polycarboxylate superplasticizer mother liquor to the reaction kettle;

[0085] (2) Add 860 parts of water for dilution;

[0086] (3) Add 20 parts of high-efficiency thickening and water-retaining agent;

[0087] (4) Add 1 part of high-performance air-entraining agent;

[0088] (5) Stir the above materials evenly to obtain the functional polycarboxylate water reducer of Example 1.

[0089] Example 2

[0090] Example 2 provides a functional polycarboxylate water reducer, and its preparation method includes:

[0091] I. Preparation of high-efficiency thickening and water-retaining agent

[0092] (1) Add 110 parts by mass of allyl polyoxyethylene ether (molecular weight: 2400), 230 parts of water, 30 parts of acrylic acid, and 4 parts of ammonium persulfate to the reaction kettle as the bottom materials in the kettle.

[0093] (2) After the bottom materials in the kettle are stirred evenly, simultaneously add dropwise Material A and Material B; Material A is a mixed solution composed of 0.3 part of vitamin C, 0.7 part of mercaptopropionic acid, and 70 parts of water; Material B is a mixed solution composed of 62 parts of acrylic acid, 0.4 part of N-hydroxymethylacrylamide, 0.4 part of N,N-methylenebisacrylamide, 12 parts of self-made functional monomer, and 60 parts of water; Material B is added dropwise for 45 minutes, and Material A is added dropwise for 60 minutes.

[0094] (3) After adding dropwise Material A, continue to stir and react for 60 minutes.

[0095] (4) After adding 420 parts of dilution water, stir the materials evenly to obtain the high-efficiency thickening and water-retaining agent.

[0096] II. Preparation of self-made functional monomer

[0097] (1) Add 550 parts by mass of hydroxyethyl acrylate to the reaction kettle.

[0098] (2) Start stirring and simultaneously raise the temperature.

[0099] (3) When the temperature of the materials rises to 40 °C, successively add 185 parts of phosphoric acid, 1.8 parts of hydroquinone, and 1.8 parts of p-toluenesulfonic acid, and simultaneously continue to raise the temperature.

[0100] (4) When the temperature rises to 95 °C, start heat preservation. The heat preservation temperature is controlled at 95 ± 5 °C, and heat preservation is carried out for 4 hours.

[0101] (5) After the heat preservation is completed, discharge the materials after the temperature drops below 45 °C to obtain the functional monomer.

[0102] III. Preparation of high-performance air-entraining agent

[0103] (1) Add 80 parts by mass of self-made high-efficiency thickening and water-retaining agent to the reaction kettle;

[0104] (2) Add 20 parts by mass of sodium lauryl polyoxyethylene ether sulfate and 12 parts by mass of Tween 20 to the reaction kettle;

[0105] (3) Add 8 parts by mass of coconut oil fatty acid diethanolamide to the reaction kettle;

[0106] (4) Uniformly mix the above materials by mechanical stirring to obtain a high-performance air-entraining agent.

[0107] IV. Preparation of polycarboxylate superplasticizer mother liquor

[0108] (1) Weigh 0.4 part of mercaptopropionic acid, 0.3 part of mercaptoacetic acid, 0.6 part of isopropanol, 0.5 part of sodium isascorbate, 0.5 part of vitamin C and 40 parts of water respectively, stir evenly, and prepare A dropping material for waiting to be used.

[0109] (2) Weigh 16 parts of acrylic acid, 4 parts of 2-acrylamido-2-methylpropanesulfonic acid, 4 parts of hydroxypropyl acrylate, 4 parts of sodium methallylsulfonate, 4 parts of self-made functional monomer and 6 parts of water respectively, stir evenly, and prepare B dropping material for waiting to be used.

[0110] (3) At room temperature, add 80 parts of water, 60 parts of isopentenyl polyoxyethylene ether, 60 parts of methyl vinyl polyoxyethylene ether, 0.6 part of hydrogen peroxide (mass percentage concentration 27.5%), 1.0 part of azodicyanovaleric acid to the reaction kettle in sequence as the bottom material of the kettle. After all the powder materials are dissolved, simultaneously add A dropping material and B dropping material dropwise. The A dropping material is added dropwise for 3.0 hours; the B dropping material is added dropwise for 2.5 hours. After adding the A dropping material dropwise, continue to stir and react for 1.0 hour, then add 15 parts of sodium hydroxide solution with a mass percentage concentration of 32% for neutralization reaction, and control the pH value of the material at 5 - 8 to discharge.

[0111] V. Preparation of functional polycarboxylate superplasticizer

[0112] (1) Add 220 parts by mass of polycarboxylate superplasticizer mother liquor to the reaction kettle;

[0113] (2) Add 900 parts of water for dilution;

[0114] (3) Add 40 parts of high-efficiency thickening and water-retaining agent;

[0115] (4) Add 3 parts of high-performance air-entraining agent;

[0116] (5) Uniformly mix the above materials to obtain the functional polycarboxylate superplasticizer of Example 2.

[0117] Example 3

[0118] Example 3 provides a functional polycarboxylate superplasticizer, and its preparation method includes:

[0119] I. Preparation of High-efficiency Thickening and Water Retaining Agent

[0120] (1) Add 100 parts by mass of allyl polyoxyethylene ether (molecular weight: 2400), 220 parts of water, 20 parts of acrylic acid, and 3 parts of ammonium persulfate as the bottom materials in the reaction kettle.

[0121] (2) After the bottom materials are stirred evenly, add Material A and Material B dropwise simultaneously; Material A is a mixed solution composed of 0.25 parts of vitamin C, 0.6 parts of mercaptopropionic acid, and 60 parts of water; Material B is a mixed solution composed of 52 parts of acrylic acid, 0.3 parts of N-hydroxymethylacrylamide, 0.3 parts of N,N-methylenebisacrylamide, 10 parts of self-made functional monomer, and 50 parts of water; Material B is added dropwise for 45 minutes, and Material A is added dropwise for 60 minutes.

[0122] (3) After adding Material A dropwise, continue stirring and reacting for 60 minutes.

[0123] (4) After adding 410 parts of dilution water, stir the materials evenly to obtain the high-efficiency thickening and water retaining agent.

[0124] II. Preparation of Self-made Functional Monomer

[0125] (1) Add 525 parts by mass of hydroxyethyl acrylate to the reaction kettle.

[0126] (2) Start stirring and heat up simultaneously.

[0127] (3) When the temperature of the materials rises to 30 °C, add 175 parts of phosphoric acid, 1.4 parts of hydroquinone, and 1.4 parts of p-toluenesulfonic acid in sequence, and continue heating up simultaneously.

[0128] (4) When the temperature rises to 95 °C, start heat preservation. The heat preservation temperature is controlled at 95 ± 5 °C, and heat preservation is carried out for 4 hours.

[0129] (5) After the heat preservation is completed, discharge the materials after the temperature drops below 45 °C to obtain the functional monomer.

[0130] III. Preparation of High-performance Air-entraining Agent

[0131] (1) Add 75 parts by mass of the self-made high-efficiency thickening and water retaining agent to the reaction kettle;

[0132] (2) Add 17.5 parts by mass of sodium lauryl polyoxyethylene ether sulfate and 9 parts by mass of Tween 20 to the reaction kettle;

[0133] (3) Add 6 parts by mass of coconut oil fatty acid diethanolamide to the reaction kettle;

[0134] Mix the above materials evenly by mechanical stirring to obtain the high-performance air-entraining agent.

[0135] IV. Preparation of Polycarboxylate Superplasticizer Mother Liquid

[0136] (1) Weigh 0.25 parts of mercaptopropionic acid, 0.2 parts of mercaptoacetic acid, 0.4 parts of isopropyl alcohol, 0.4 parts of sodium erythorbate, 0.3 parts of vitamin C and 32.5 parts of water respectively, stir evenly, and prepare A dropping material for waiting to be used.

[0137] (2) Weigh 13 parts of acrylic acid, 2.5 parts of 2 - acrylamido - 2 - methylpropanesulfonic acid, 2.5 parts of hydroxypropyl acrylate, 2.5 parts of sodium methallylsulfonate and 2.5 parts of self - made functional monomer, 4 parts of water respectively, stir evenly, and prepare B dropping material for waiting to be used.

[0138] (3) At room temperature, add 70 parts of water, 50 parts of isopentenyl polyoxyethylene ether, 50 parts of methallyl polyoxyethylene ether, 0.4 parts of hydrogen peroxide (mass percentage concentration 27.5%), 0.8 parts of azodicyanovaleric acid into the reaction kettle in sequence as the bottom material of the kettle. After all the powder materials are dissolved, simultaneously add A dropping material and B dropping material. The dropping time of A dropping material is 3.0 hours; the dropping time of B dropping material is 2.5 hours. After adding A dropping material, continue to stir and react for 1.0 hour, then add 13 parts of sodium hydroxide solution with a mass percentage concentration of 32% for neutralization reaction, and control the pH value of the material at 5 - 8 to discharge.

[0139] V. Preparation of Functional Polycarboxylate Superplasticizer

[0140] (1) Add 200 parts by mass of polycarboxylate superplasticizer mother liquid into the reaction kettle;

[0141] (2) Add 880 parts of water for dilution;

[0142] (3) Add 30 parts of high - efficiency thickening and water - retaining agent;

[0143] (4) Add 2 parts of high - performance air - entraining agent;

[0144] (5) Stir the above materials evenly to obtain the functional polycarboxylate superplasticizer of Example 3.

[0145] Comparative Example 1

[0146] Comparative Example 1 provides a functional polycarboxylate superplasticizer. The difference in its preparation method from that of Example 1 is that Comparative Example 1 uses conventional functional monomers instead of the self - made functional monomer in this application. Conventional functional monomers refer to commonly used hydroxyethyl acrylate in the market and various anti - mud functional monomers used in the industry. For example, Comparative Example 1 uses the anti - mud functional monomer of Wuhan Blue Ribbon New Materials Co., Ltd. (Model: LD201), and other steps and parameters are the same as those of Example 1.

[0147] Comparative Example 2

[0148] Comparative Example 2 provides a functional polycarboxylate water reducer, and the difference in its preparation method from that of Example 1 lies in that: the air-entraining agent in Comparative Example 2 does not contain the self-made thickening and water-retaining agent of the present application, and other steps and parameters are the same as those in Example 1.

[0149] The performance test results of the functional polycarboxylate water reducers of each example and comparative example and similar products on the market are shown in Table 1.

[0150] Table 1 Performance comparison of the functional polycarboxylate water reducers of each example and comparative example

[0151]

[0152]

[0153] It can be seen from the data in Table 1 above that the performance of the functional polycarboxylate water reducer of the present application is significantly better than that of similar products on the market and the products of Comparative Example 1 and Comparative Example 2. Among them, the performance of the functional polycarboxylate water reducer in Example 3 is the best, with a bleeding rate of 20%; an air content of 4.0%; a slump loss after 1 hour of +10 mm; compared with existing similar products on the market, it has the obvious characteristic of better mechanical properties, and the water-reducing rate of the fresh concrete is high, the fluidity is good, and the concrete is easy to be pumped for construction.

[0154] Finally, it should be noted that: the above embodiments are only used to illustrate the technical solutions of the present application, rather than to limit them; although the present application has been described in detail with reference to the foregoing embodiments, those of ordinary skill in the art should understand that: they can still modify the technical solutions recorded in the foregoing embodiments, or perform equivalent replacements on some or all of the technical features; and these modifications or replacements do not make the essence of the corresponding technical solutions deviate from the scope of the technical solutions of the embodiments of the present application.

[0155] In addition, those skilled in the art can understand that although some embodiments herein include certain features included in other embodiments rather than other features, the combination of the features of different embodiments means that it is within the scope of the present application and forms different embodiments. For example, in the claims above, any one of the claimed embodiments can be used in any combination. The information disclosed in this background art section is only intended to deepen the understanding of the overall background art of the present application, and should not be regarded as an admission or any form of suggestion that this information constitutes prior art already known to those skilled in the art.

Claims

1. A functional polycarboxylate water reducer, characterized in that, By mass parts, it includes: 180 - 220 parts of polycarboxylate superplasticizer mother liquor, 860 - 900 parts of water, 20 - 40 parts of thickening and water - retaining agent, and 1 - 3 parts of air - entraining agent.

2. The functional polycarboxylate water reducer according to claim 1, wherein The polycarboxylate superplasticizer mother liquor, the thickening and water - retaining agent, and the air - entraining agent all include functional monomers; The functional monomers, by mass parts, include: 500 - 550 parts of hydroxyethyl acrylate, 165 - 185 parts of phosphoric acid, 1.0 - 1.8 parts of hydroquinone, and 1.0 - 1.8 parts of p - toluenesulfonic acid.

3. The functional polycarboxylate water reducer according to claim 2, characterized in that, The thickening and water - retaining agent, by mass parts, includes: 90 - 110 parts of methyl allyl polyoxyethylene ether, 10 - 30 parts of acrylic acid, 2 - 4 parts of ammonium persulfate, 0.2 - 0.3 parts of vitamin C, 0.5 - 0.7 parts of mercaptopropionic acid, 42 - 62 parts of acrylic acid, 0.2 - 0.4 parts of N - hydroxymethyl acrylamide, 0.2 - 0.4 parts of N,N - methylene bisacrylamide, 8 - 12 parts of functional monomers, and 700 - 780 parts of water.

4. The functional polycarboxylate water reducing agent according to claim 3, characterized in that, The air - entraining agent, by mass parts, includes: 70 - 80 parts of thickening and water - retaining agent, 15 - 20 parts of sodium lauryl polyoxyethylene ether sulfate, 6 - 12 parts of Tween 20, and 4 - 8 parts of coconut oil fatty acid diethanolamide.

5. The functional polycarboxylate water reducer according to claim 4, characterized in that, The polycarboxylate superplasticizer mother liquor, by mass parts, includes: 0.1 - 0.4 parts of mercaptopropionic acid, 0.1 - 0.3 parts of mercaptoacetic acid, 0.2 - 0.6 parts of isopropyl alcohol, 0.3 - 0.5 parts of sodium isascorbate, 0.1 - 0.5 parts of vitamin C, 10 - 16 parts of acrylic acid, 1 - 4 parts of 2 - acrylamido - 2 - methylpropane sulfonic acid, 1 - 4 parts of hydroxypropyl acrylate, 1 - 4 parts of sodium methallyl sulfonate, 1 - 4 parts of functional monomers, 40 - 60 parts of isopentenyl polyoxyethylene ether, 40 - 60 parts of methyl vinyl polyoxyethylene ether, 0.2 - 0.6 parts of hydrogen peroxide, 0.6 - 1.0 parts of azodicyanovaleric acid, 11 - 15 parts of sodium hydroxide solution, and 87 - 126 parts of water.

6. The functional polycarboxylate water reducer according to claim 5, wherein The mass percentage concentration of the hydrogen peroxide is 27.5%, the mass percentage concentration of the sodium hydroxide solution is 32%, and the pH value of the polycarboxylate superplasticizer mother liquor is 5 - 8.

7. A preparation method of the functional polycarboxylate water reducer as described in claim 5, characterized in that, It includes: Prepare the polycarboxylate superplasticizer mother liquor, the thickening and water - retaining agent, and the air - entraining agent separately, and stir the polycarboxylate superplasticizer mother liquor, the thickening and water - retaining agent, the air - entraining agent and water evenly to obtain the functional polycarboxylate superplasticizer.

8. The preparation method of the functional polycarboxylate water reducer according to claim 7, characterized in that, The preparation method of the thickening and water - retaining agent includes: Add methyl allyl polyoxyethylene ether, 210 - 230 parts of water, acrylic acid, and ammonium persulfate into the reaction kettle as the bottom materials; after the bottom materials are stirred evenly, simultaneously drip material A and material B; material A is a mixed solution composed of vitamin C, mercaptopropionic acid, and 50 - 70 parts of water; material B is a mixed solution composed of acrylic acid, N - hydroxymethyl acrylamide, N,N - methylene bisacrylamide, functional monomers, and 40 - 60 parts of water; after dripping, add 400 - 420 parts of water, and stir the materials evenly to obtain the thickening and water - retaining agent; The preparation method of the functional monomers includes: Add hydroxyethyl acrylate to the reaction kettle. When the material temperature rises to 30°C - 40°C, add phosphoric acid, hydroquinone, and p-toluenesulfonic acid in sequence. Then continue to heat up to 95°C and keep the temperature at 95 ± 5°C for insulation. After 4 hours of insulation, when the temperature drops below 45°C, the functional monomer is obtained.

9. The preparation method of the functional polycarboxylate water reducing agent according to claim 8, wherein, The preparation method of the air-entraining agent includes: Add a thickening and water-retaining agent, sodium lauryl polyoxyethylene ether sulfate, Tween 20, and coconut oil fatty acid diethanolamide to the reaction kettle, and stir the above materials evenly to obtain the air-entraining agent; The preparation method of the polycarboxylate superplasticizer mother liquor includes: Stir mercaptopropionic acid, mercaptoacetic acid, isopropanol, sodium isascorbate, vitamin C, and 25 - 40 parts of water evenly to prepare a dropping material A; Stir acrylic acid, 2-acrylamido-2-methylpropanesulfonic acid, hydroxypropyl acrylate, sodium methallylsulfonate, the functional monomer, and 2 - 6 parts of water evenly to prepare a dropping material B; Add 60 - 80 parts of water, isopentenyl polyoxyethylene ether, methyl vinyl polyoxyethylene ether, hydrogen peroxide, and azodicyanovaleric acid to the reaction kettle as the bottom material of the kettle. After the powder is dissolved completely, add dropping material A and dropping material B simultaneously. After the dropping is completed, add sodium hydroxide solution to adjust the pH value to 5 - 8 to obtain the polycarboxylate superplasticizer mother liquor.

10. Application of a functional polycarboxylate superplasticizer according to any one of claims 1 to 6 in the preparation of concrete.

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