CN113429512A - Application of water-soluble polymer as curing agent in cement-based material - Google Patents
Application of water-soluble polymer as curing agent in cement-based material Download PDFInfo
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- CN113429512A CN113429512A CN202110613588.8A CN202110613588A CN113429512A CN 113429512 A CN113429512 A CN 113429512A CN 202110613588 A CN202110613588 A CN 202110613588A CN 113429512 A CN113429512 A CN 113429512A
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- acrylamide
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- cement
- polyacrylamide
- acrylate
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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
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/52—Amides or imides
- C08F220/54—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide
- C08F220/56—Acrylamide; Methacrylamide
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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
- C04B24/2652—Nitrogen containing polymers, e.g. polyacrylamides, polyacrylonitriles
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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
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Ceramic Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Structural Engineering (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Curing Cements, Concrete, And Artificial Stone (AREA)
Abstract
The application discloses an application of a water-soluble polymer as a curing agent in a cement-based material, wherein the water-soluble polymer is hydrolyzed polyacrylamide. The application improves the application performance of the water-soluble high-molecular polyacrylamide in the field of building materials, reduces the influence of the common polyacrylamide materials on the hydration heat of cement, obviously reduces the hydration heat release of the obtained cement materials, relieves the cracking condition of the cement, and is beneficial to prolonging the service life of cement mortar.
Description
Technical Field
The application relates to an application of a water-soluble polymer as a curing agent in a cement-based material, belonging to the technical field of curing of the cement-based material.
Background
Admixture is adopted in the market at present to improve the performance of cement so as to save cost. Hydrotalcite, flyash and nano CaCO3Carbon nanotubes, Cellulose Ethers (CE), polyacrylamides, etc. have been used as admixtures for improving silicate waterProperties of the mud. Wherein, the CE is used as an internal curing agent to modify mortar and coagulate, which can reduce the heat release of early hydration of cement, delay the hydration kinetic process of cement and increase the critical tension of cement slurry. But the cellulose ether polymer has higher cost, more complex synthetic method and low economic benefit; the water retention capacity of the common polyacrylamide applied to cement mortar is poor.
The water-soluble polymer can improve the performance of the portland cement. Wherein, the polyacrylamide has the advantages of viscosity increasing and good water solubility, and can be used as an internal curing agent to be applied to cement-based materials. Hydrophilic groups in the polyacrylamide can be associated with water molecules of the cement-based material to form hydrogen bonds, so that the bleeding degree of the material is reduced, the viscosity of the mortar can be increased after the material is dissolved, and the consistency of the material is reduced; the polyacrylamide polymer can be hydrolyzed in water to generate carboxylic acid ions which are complexed with various cations such as calcium, magnesium and the like in cement water to form a stable product, which is beneficial to improving the hardness of cement paste; after being dissolved, the polyacrylamide is wrapped on unhydrated cement minerals and hydration products, simultaneously the appearance of the hydration products of the cement is changed, the hydration heat release of the cement is reduced, and the problem of cement cracking is further improved.
Disclosure of Invention
According to one aspect of the present application, there is provided the use of a water-soluble polymer which is a hydrolyzed polyacrylamide as a curing agent in a cement-based material. The application provided by the application solves the problem of improving the application performance of water-soluble high-molecular polyacrylamide in the field of building materials, reduces the influence of the conventional common polyacrylamide materials on the hydration heat of cement, obviously reduces the hydration heat release of the obtained cement material, relieves the cracking condition of the cement, and is beneficial to prolonging the service life of cement mortar.
The application of a water-soluble polymer as a curing agent in a cement-based material is characterized in that the water-soluble polymer is hydrolyzed polyacrylamide.
Optionally, the hydrolysis degree of the hydrolyzed polyacrylamide is 15-25%; the relative molecular mass is 1300-1700 ten thousand; the viscosity is 150-220 cp.
Optionally, the upper limit of the degree of hydrolysis is selected from 18%, 20%, 22%, 25%; the lower limit is selected from 15%, 18%, 20%, 22%.
Alternatively, the upper relative molecular weight limit is selected from 1400, 1500, 1600, 1700 ten thousand; the lower limit is selected from 1300 ten thousand, 1400 ten thousand, 1500 ten thousand and 1600 ten thousand.
Optionally, the upper viscosity limit is selected from 160, 170, 180, 190, 200 cp; the lower limit is selected from 150, 160, 170, 180, 190 cp.
Alternatively, the hydrolyzed polyacrylamide is prepared by the following steps:
reacting raw materials containing an acrylamide compound, acrylate and an initiator to obtain the hydrolyzed polyacrylamide;
the acrylamide-based compound includes acrylamide.
Optionally, the acrylate salt comprises sodium acrylate;
the initiator comprises at least one of an oxidizing agent and a reducing agent.
Optionally, the oxidizing agent comprises at least one of potassium persulfate, azobisisobutyronitrile;
the reducing agent comprises sodium bisulfite.
Alternatively, the initiator comprises potassium persulfate, sodium bisulfite, and azobisisobutyronitrile.
Optionally, the mass ratio of the potassium persulfate to the sodium bisulfite to the azobisisobutyronitrile is 0.1-0.5: 0.05-0.3: 0.1 to 0.5.
Optionally, the mass ratio of the acrylate to the acrylamide is 15-25: 75-100 parts;
the mass ratio of the initiator to the acrylamide is 0.1-0.5: 75-100 parts;
the mass ratio of the sum of the mass of the acrylate and the mass of the acrylamide to the mass of the raw materials is 15-25: 100.
optionally, the upper limit of the mass ratio of the acrylate to the acrylamide is selected from 17: 75-100, 18: 75-100, 22: 75-100, 23: 75-100, 24: 75-100 or 25: 75-100 parts; the lower limit is selected from 15: 75-100, 18: 75-100, 20: 75-100, 22: 75-100, 23: 75-100 or 24: 75-100 parts.
Optionally, the mass ratio of the acrylate to the acrylamide is 15-25: 75-80 parts.
Optionally, the mass ratio of the acrylate to the acrylamide is 15-20: 75-80 parts.
Optionally, the mass ratio of the acrylate to the acrylamide is 15-25: 75.
optionally, the mass ratio of the initiator to the acrylamide is 0.3-0.5: 75-90;
optionally, the mass ratio of the initiator to the acrylamide is 0.3-0.5: 75.
optionally, the upper limit of the mass ratio of the sum of the mass of the acrylate and the mass of the acrylamide to the raw material is selected from 17: 100. 19: 100. 21: 100. 23: 100 or 25: 100, respectively; the lower limit is selected from 15: 100. 17: 100. 19: 100. 21: 100 or 23: 100.
optionally, the acrylamide compound further includes 2-acrylamide-2-methylpropanesulfonic acid salt.
Alternatively, the 2-acrylamido-2-methylpropanesulfonic acid salt comprises sodium 2-acrylamido-2-methylpropanesulfonic acid salt.
Optionally, the mass ratio of the 2-acrylamide-2-methylpropanesulfonic acid salt to the acrylamide is 5-10: 100.
alternatively, the upper limit of the mass ratio of the 2-acrylamido-2-methylpropanesulfonic acid salt to the acrylamide is selected from 6: 100. 7: 100. 8: 100 or 10: 100, respectively; the lower limit is selected from 5: 100. 6: 100. 7: 100 or 8: 100.
optionally, the feedstock also contains water.
Optionally, the conditions of the reaction include: under the heat insulation condition, the initial temperature is 0-30 ℃.
Optionally, the upper initial temperature limit is selected from 5 ℃, 8 ℃, 10 ℃, 15 ℃, 17 ℃, 20 ℃, 22 ℃, 25 ℃, or 30 ℃; the lower limit is selected from 0 deg.C, 5 deg.C, 8 deg.C, 10 deg.C, 15 deg.C, 17 deg.C, 20 deg.C, 22 deg.C or 25 deg.C.
Optionally, the conditions of the reaction include: under the condition of inactive gas, the pH value is 7-13, and the reaction time is 6-10 h.
Optionally, the upper pH limit is 8, 9, 11, or 13; the lower limit is 7, 8, 9 or 11.
Optionally, the upper reaction time limit is selected from 7, 8, 9, or 10 h; the lower limit is selected from 6, 7, 8 or 9 h.
Alternatively, the hydrolyzed polyacrylamide is prepared by the following steps:
(S1) mixing raw materials containing acrylamide, acrylate, 2-acrylamido-2-methylpropanesulfonate and water to obtain a mixture I;
(S2) adjusting the pH value of the mixture I to 7-13, adding an initiator, and reacting to obtain the hydrolyzed polyacrylamide.
Optionally, the application comprises the steps of:
the raw materials containing hydrolytic polyacrylamide, cement-based materials and water are subjected to hydration reaction.
Optionally, the mass ratio of the hydrolyzed polyacrylamide to the cement-based material to the water is 0.01-0.2: 50-100: 50.
optionally, the mass ratio of the hydrolyzed polyacrylamide to the cement-based material to the water is 0.01-0.2: 100: 50.
optionally, the time of the hydration reaction is 72-120 h.
Optionally, the time of the hydration reaction is 100-120 h.
According to one aspect of the application, a water-soluble polymer, a preparation method and application thereof are provided, and the problem of overhigh heat release of cement hydration is solved.
A process for the preparation of said water-soluble polymer, said process comprising at least the following steps:
carrying out polymerization reaction on a mixture containing an acrylamide monomer, 2-acrylamide-2-methylpropanesulfonate, acrylate and the like in the presence of an initiator to obtain a water-soluble polymer;
the initiator includes an oxidizing agent.
The dosage of the acrylate monomer is 20-25% of the mass of the acrylamide monomer.
The dosage of the 2-acrylamide-2-methylpropanesulfonate accounts for 5-10% of the mass of the acrylamide monomer.
Optionally, the mixture further comprises a solvent, the solvent being water;
the sum of the total mass of the acrylamide monomer and the acrylate monomer accounts for 15-25% of the mass of the whole system.
Optionally, the method comprises:
(S1) mixing an acrylamide monomer, a sodium acrylate monomer, 2-acrylamide-2-methyl sodium propanesulfonate and water, and uniformly mixing to obtain a mixture I;
(S2) adjusting the pH value of the mixture I to 8-13, then adding an initiator into the mixture I, uniformly mixing, and carrying out polymerization reaction to obtain the water-soluble high polymer.
The pH value is adjusted by using an alkaline solution, which is not particularly limited in the application, and in the specific implementation process, the technology in the art can select the alkaline solution with corresponding concentration according to the requirement, such as a sodium hydroxide solution, a sodium carbonate solution and the like,
alternatively, the conditions of the polymerization reaction are:
the initial reaction temperature is 0-30 ℃, and the reaction time is 6-10 h;
preferably, the polymerization is carried out under an inert gas blanket.
Preferably, the reaction is carried out under adiabatic conditions, i.e. without heat exchange with the outside during the reaction.
Preferably, the inert gas used may be nitrogen, argon, or the like.
Specifically, the lower limit of the initial reaction temperature may be independently selected from 0 ℃, 5 ℃, 8 ℃, 10 ℃, 15 ℃; the upper limit of the initial reaction temperature may be independently selected from the group consisting of 17 deg.C, 20 deg.C, 22 deg.C, 25 deg.C, and 30 deg.C.
Specifically, the reaction time can be independently selected from 6h, 7h, 8h, 9h and 10 h.
According to yet another aspect of the present application, there is provided a water-soluble polymer prepared by any one of the above-mentioned preparation methods.
According to yet another aspect of the present application, there is provided a use of a water-soluble polymer in the field of construction materials.
Optionally, the above application comprises at least the following steps:
granulating the water-soluble polymer to obtain polymer particles;
and drying and crushing the polymer particles to obtain the cement internal curing agent.
The water-soluble polymer is mixed with 50g of benchmark cement and 25g of water to carry out hydration reaction for 120 hours.
Specifically, the amount of the water-soluble polymer to be incorporated may be independently selected from the group consisting of 0.005g, 0.01g, 0.05g and 0.1 g.
The beneficial effects that this application can produce include:
(1) the application provided by the application improves the application performance of the water-soluble high-molecular polyacrylamide in the field of building materials.
(2) The application provided by the application reduces the influence of the conventional common polyacrylamide materials on the hydration heat of cement, obviously reduces the hydration heat release of the obtained cement materials, relieves the cracking condition of the cement, and is beneficial to prolonging the service life of cement mortar.
(3) The salt tolerance of the hydrolyzed polyacrylamide can be improved by adding 2-acrylamide-2-methylpropanesulfonate.
(4) The application provided by the application has the advantages that the adopted raw materials are low in price, and the preparation method is convenient, simple and easy to operate.
Detailed Description
The present application will be described in detail with reference to examples, but the present application is not limited to these examples.
The raw materials in the examples of the present application were all purchased commercially, unless otherwise specified.
Example 1
Preparation of hydrolysis type polyacrylamide:
(S1) mixing 75g of acrylamide monomer, 20g of sodium acrylate monomer, 5g of 2-acrylamide-2-methyl sodium propanesulfonate and 400g of water, and uniformly mixing to obtain a mixture I;
(S2) adjusting the pH value of the mixture I to 7 by using a sodium hydroxide solution with the concentration of 2mol/L, then adding 0.2g of potassium persulfate, 0.1g of sodium bisulfite and 0.2g of azobisisobutyronitrile into the mixture I, uniformly mixing, and carrying out adiabatic polymerization under the condition of a nitrogen atmosphere, wherein the initial reaction temperature is 20 ℃, and the reaction time is 6 hours, so as to obtain the hydrolysis type polyacrylamide.
Examples 2 to 3
Preparation of hydrolysis type polyacrylamide:
the preparation methods of examples 2 to 3 are different from example 1 only in that they are shown in the following Table 1
TABLE 1 differences between examples 2 to 3 and example 1
Characterization of hydrolyzed Polyacrylamide
And (3) determining the degree of hydrolysis: the assay was carried out according to GB/T12005.6-1989.
Relative molecular mass determination: the determination is carried out according to GB/T12005.10-1992.
And (3) viscosity measurement: : the hydrolyzed polyacrylamide was dissolved in saline to a concentration of 1500ppm and the viscosity was measured at 7.314s-1 by a rheometer.
The measurement results are shown in table 2:
TABLE 2 measurement results of degree of hydrolysis, relative molecular weight, and viscosity
Determination of hydrolysis type polyacrylamide Property
50g of standard cement and 25g of water were mixed with 0.05g of a hydrolyzed polyacrylamide having a hydrolysis degree of 15% (the hydrolyzed polyacrylamide prepared in example 2), 20% (the hydrolyzed polyacrylamide prepared in example 1) and 25% (the hydrolyzed polyacrylamide prepared in example 3), respectively, and subjected to hydration reaction for 120 hours, and the hydration heat release during hydration was measured, and the addition of partially hydrolyzed polyacrylamide reduced the hydration heat release efficiency of the cement during the deceleration period and the stabilization period, and the addition of the partially hydrolyzed polyacrylamide reduced the hydration heat release efficiency of the cement by 6.5% for the polyacrylamide having a hydrolysis degree of 15%, by 10% for the polyacrylamide having a hydrolysis degree of 20%, and by 8% for the polyacrylamide having a hydrolysis degree of 25%.
Comparative example 1:
ordinary polyacrylamide preparation:
(S1) mixing 95g of acrylamide monomer, 5g of sodium 2-acrylamide-2-methylpropanesulfonate and 400g of water, and uniformly mixing to obtain a mixture I;
(S2) adjusting the pH value of the mixture I to 7 by using a sodium hydroxide solution with the concentration of 2mol/L, then adding 0.2g of potassium persulfate, 0.1g of sodium bisulfite and 0.2g of azobisisobutyronitrile into the mixture I, uniformly mixing, and carrying out heat insulation polymerization reaction under the condition of nitrogen atmosphere, wherein the reaction initial temperature is 20 ℃ and the reaction time is 2 hours, so as to obtain the hydrolysis type polyacrylamide.
The ordinary polyacrylamide of comparative example 1 was autonomously synthesized by my own, and 0.05g of the ordinary polyacrylamide of comparative example 1 was added to 50g of the reference cement and 25g of water, respectively, to perform a hydration reaction for 120 hours, which reduced the total hydration heat release by less than 2%.
Although the present application has been described with reference to a few embodiments, it should be understood that various changes, substitutions and alterations can be made herein without departing from the spirit and scope of the application as defined by the appended claims.
Claims (10)
1. The application of the water-soluble polymer as the curing agent in the cement-based material is characterized in that the water-soluble polymer is hydrolyzed polyacrylamide.
2. The use according to claim 1, wherein the hydrolysis degree of the hydrolyzed polyacrylamide is 15-25%; the relative molecular weight is 1300-1700 ten thousand; the viscosity is 150-200 cp.
3. The use according to claim 1, wherein the hydrolyzed polyacrylamide is prepared by the following steps:
reacting raw materials containing an acrylamide compound, acrylate and an initiator to obtain the hydrolyzed polyacrylamide;
the acrylamide-based compound includes acrylamide;
preferably, the acrylate salt comprises sodium acrylate;
the initiator comprises at least one of an oxidizing agent and a reducing agent;
preferably, the oxidizing agent comprises at least one of potassium persulfate and azobisisobutyronitrile;
the reducing agent comprises sodium bisulfite.
4. The use according to claim 3, wherein the mass ratio of the acrylate to the acrylamide is 15-25: 75-100 parts;
the mass ratio of the initiator to the acrylamide is 0.1-0.5: 75-100 parts;
the mass ratio of the sum of the mass of the acrylate and the mass of the acrylamide to the mass of the raw materials is 15-25: 100.
5. the use according to claim 3, wherein the acrylamide-based compound further comprises 2-acrylamido-2-methylpropanesulfonate;
preferably, the 2-acrylamido-2-methylpropanesulfonic acid salt comprises sodium 2-acrylamido-2-methylpropanesulfonic acid salt;
preferably, the mass ratio of the 2-acrylamide-2-methylpropanesulfonic acid salt to the acrylamide is 5-10: 100.
6. use according to claim 3, wherein the feedstock further comprises water.
7. Use according to claim 3, characterized in that the conditions of the reaction comprise: under the heat insulation condition, the initial temperature is 0-30 ℃.
8. Use according to claim 3, characterized in that the conditions of the reaction comprise: under the condition of inactive gas, the pH value is 7-13, and the reaction time is 6-10 h.
9. The use according to claim 3, wherein the hydrolyzed polyacrylamide is prepared by the following steps:
(S1) mixing raw materials containing acrylamide, acrylate, 2-acrylamido-2-methylpropanesulfonate and water to obtain a mixture I;
(S2) adjusting the pH value of the mixture I to 7-13, adding an initiator, and reacting to obtain the hydrolyzed polyacrylamide.
10. The application according to claim 1, characterized in that it comprises the following steps:
carrying out hydration reaction on raw materials containing hydrolytic polyacrylamide, a cement-based material and water;
preferably, the mass ratio of the hydrolyzed polyacrylamide to the cement-based material to the water is 0.01-0.2: 50-100: 50;
preferably, the time of the hydration reaction is 72-120 h.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN115353352A (en) * | 2022-09-01 | 2022-11-18 | 中德新亚建筑材料有限公司 | Anti-static non-ignition fine aggregate concrete for nuclear power plant and preparation method thereof |
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| US4015991A (en) * | 1975-08-08 | 1977-04-05 | Calgon Corporation | Low fluid loss cementing compositions containing hydrolyzed acrylamide/2-acrylamido-2-methylpropane sulfonic acid derivative copolymers and their use |
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| CN115353352A (en) * | 2022-09-01 | 2022-11-18 | 中德新亚建筑材料有限公司 | Anti-static non-ignition fine aggregate concrete for nuclear power plant and preparation method thereof |
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