CN111362616A - Concrete water reducing agent and preparation method thereof - Google Patents
Concrete water reducing agent and preparation method thereof Download PDFInfo
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- CN111362616A CN111362616A CN202010314622.7A CN202010314622A CN111362616A CN 111362616 A CN111362616 A CN 111362616A CN 202010314622 A CN202010314622 A CN 202010314622A CN 111362616 A CN111362616 A CN 111362616A
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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
- C04B24/28—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- C04B24/32—Polyethers, e.g. alkylphenol polyglycolether
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- 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
- 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 relates to a concrete water reducing agent which is characterized by being prepared from the following raw materials in parts by weight: 10-20 parts of carboxyl modified N-vinylcarbazole/polyethylene glycol monoallyl ether/5-vinyl-1, 2, 4-oxadiazole-3-ethyl carboxylate copolymer, 5-10 parts of 3-aminopyrazine-2-carboxylic acid modified epoxy-terminated hyperbranched poly (amine-ester), 2-4 parts of rare earth metal organic framework, 3-6 parts of N-sulfochitosan and 30-40 parts of water. The invention also provides a preparation method of the concrete water reducing agent. The concrete water reducing agent disclosed by the invention is low in mixing amount, high in water reducing performance, good in plasticizing effect and good in adaptability with concrete, has no negative influence on the comprehensive performance of the concrete, can obviously improve the fluidity and the working performance of the cement concrete of machine-made sand, improves the strength, the durability and the thawing resistance of the concrete, and is good in adaptability with the concrete.
Description
Technical Field
The invention relates to the technical field of concrete admixtures, in particular to a concrete water reducing agent and a preparation method thereof.
Background
In recent years, with economic development and social progress, the living standard of people is improved year by year, and the demand for improving the living environment is more and more urgent. It is in this situation that various major construction projects, which are a sign of urban modernization, are proposed in succession, which are the symbols of modern civilization. The use of concrete materials, referred to as "concrete" for short, is not left behind these major construction projects, and generally refers to an important building material obtained by mixing cement as a cementing material, sand and stone as an aggregate with water in a certain proportion and stirring. The quality of the concrete material directly influences the quality of the construction engineering. Therefore, it is very important to develop concrete materials with excellent comprehensive properties.
In order to improve the overall properties of concrete materials, concrete additives are usually added before or during the mixing of the concrete materials. The addition of additives to concrete materials to improve and improve the strength, fluidity, durability and impermeability of the concrete materials is an effective measure for improving the related properties of the concrete materials. The concrete additives in the prior art are more in variety, wherein the most important one is a concrete water reducing agent which can reduce the water consumption for mixing and improve the concrete strength under the condition of unchanged concrete workability and cement consumption; or the cement consumption is saved under the condition of unchanged workability and strength. However, the water reducing agent used in the current market has the defects of large mixing amount, poor water reducing property, poor plasticizing effect, single function, easy deterioration, easy mildew growth and deterioration in the storage and transportation process, subsequent odor generation, performance reduction in the light case and complete loss of efficacy in the heavy case, and cannot meet the market requirements; moreover, the problems of compatibility of the water reducing agent and other concrete additives in the prior art, performance reduction of the traditional water reducing agent caused by the content of soil in the sandstone material and the like are particularly prominent in the practical application process.
Chinese invention patent CN104119026B discloses a concrete composite water reducing agent, which is prepared by mixing the following raw materials of sulfanilate-sulfonated acetone-formaldehyde condensate, β -naphthalenesulfonate formaldehyde condensate, petroleum sulfonate, calcium lignosulfonate, aminotriethanol, sulfonate type waterborne polyurethane, zinc phosphate, ash calcium powder, polyvinylpyrrolidone, sodium silicate, cinder, triterpenoid saponin, allyl thiourea, rhamnolipid, isooctyl triethoxysilane and an auxiliary agent.
Therefore, the development of the concrete water reducing agent which has low mixing amount, high water reducing property, good plasticizing effect and no negative influence on the comprehensive performance of concrete, can obviously improve the fluidity and the working performance of the cement concrete of the machine-made sand, improves the strength, the durability and the thawing resistance of the concrete, meets the market demand with the concrete water reducing agent with good adaptability, and has very important significance for promoting the development of the concrete additive industry.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide a concrete water reducing agent and a preparation method thereof. The concrete water reducing agent prepared by the preparation method has low mixing amount, high water reducing property, good plasticizing effect and no negative influence on the comprehensive performance of the concrete, can obviously improve the fluidity and the working performance of the cement concrete of the machine-made sand, improves the strength, the durability and the frost resistance of the concrete, and has good adaptability to the concrete.
In order to achieve the purpose, the invention adopts the technical scheme that:
the concrete water reducing agent is characterized by being prepared from the following raw materials in parts by weight: 10-20 parts of carboxyl modified N-vinylcarbazole/polyethylene glycol monoallyl ether/5-vinyl-1, 2, 4-oxadiazole-3-ethyl carboxylate copolymer, 5-10 parts of 3-aminopyrazine-2-carboxylic acid modified epoxy-terminated hyperbranched poly (amine-ester), 2-4 parts of rare earth metal organic framework, 3-6 parts of N-sulfochitosan and 30-40 parts of water.
Preferably, the preparation method of the carboxyl modified N-vinylcarbazole/polyethylene glycol monoallyl ether/5-vinyl-1, 2, 4-oxadiazole-3-carboxylic acid ethyl ester copolymer comprises the following steps:
step S1, adding N-vinylcarbazole, polyethylene glycol monoallyl ether, 5-vinyl-1, 2, 4-oxadiazole-3-carboxylic acid ethyl ester and an initiator into a high-boiling-point solvent, stirring and reacting for 4-6 hours at 65-75 ℃ in a nitrogen or inert gas atmosphere, and then removing the solvent by rotary evaporation to obtain an N-vinylcarbazole/polyethylene glycol monoallyl ether/5-vinyl-1, 2, 4-oxadiazole-3-carboxylic acid ethyl ester copolymer;
step S2, adding the N-vinylcarbazole/polyethylene glycol monoallyl ether/5-vinyl-1, 2, 4-oxadiazole-3-carboxylic acid ethyl ester copolymer prepared in the step S1 into N-methylpyrrolidone, adding chloropropionic acid and a basic catalyst into the N-methylpyrrolidone, stirring the mixture at the temperature of 70-80 ℃ for reacting for 4-6 hours, and then removing the N-methylpyrrolidone by rotary evaporation; and dissolving the obtained crude product in water to form a solution, adding the solution into a dialysis bag, dialyzing in deionized water for 10-20 hours, and then performing rotary evaporation on the solution in the dialysis bag to remove water to obtain the product.
Preferably, the mass ratio of the N-vinylcarbazole, the polyethylene glycol monoallyl ether, the ethyl 5-vinyl-1, 2, 4-oxadiazole-3-carboxylate, the initiator and the high-boiling point solvent in the step S1 is 1:2 (0.1-0.4): 0.03-0.04): 12-20.
Preferably, the initiator is at least one of azobisisobutyronitrile and azobisisoheptonitrile.
Preferably, the high boiling point solvent is at least one of dimethyl sulfoxide, N-dimethylformamide, N-dimethylacetamide and N-methylpyrrolidone.
Preferably, the mass ratio of the N-vinylcarbazole/polyethylene glycol monoallyl ether/5-vinyl-1, 2, 4-oxadiazole-3-carboxylic acid ethyl ester copolymer, the N-methylpyrrolidone, the chloropropionic acid and the basic catalyst in the step S2 is 1 (5-10): 0.2-0.4: 0.4-0.7.
Preferably, the alkaline catalyst is at least one of sodium hydroxide, potassium hydroxide, sodium carbonate and potassium carbonate.
Further, the preparation method of the 3-aminopyrazine-2-carboxylic acid modified epoxy end group hyperbranched poly (amine-ester) comprises the following steps: adding 3-aminopyrazine-2-carboxylic acid and epoxy end group hyperbranched poly (amine-ester) into N, N-dimethylformamide, stirring and reacting for 6-8 hours at 80-90 ℃, and then removing the N, N-dimethylformamide by rotary evaporation to obtain the 3-aminopyrazine-2-carboxylic acid modified epoxy end group hyperbranched poly (amine-ester).
Preferably, the mass ratio of the 3-aminopyrazine-2-carboxylic acid to the epoxy end group hyperbranched poly (amine-ester) to the N, N-dimethylformamide is 1 (4-7) to (20-30).
Preferably, the epoxy-terminated hyperbranched poly (amine-ester) is prepared by the method comprising: chinese patent application No. 200910067539.8, example 8.
Preferably, the preparation method of the rare earth metal organic framework is described in chinese patent application No. 201210245269.7, example 1.
Preferably, the preparation method of the N-sulfochitosan is described in Chinese patent application No. 03129053.1, example 1.
The invention also aims to provide a preparation method of the concrete water reducing agent, which is characterized by comprising the following steps: the raw materials are uniformly mixed according to the parts by weight, and are stirred and reacted for 4 to 7 hours at the temperature of between 45 and 60 ℃ to obtain the concrete water reducer.
Due to the application of the technical scheme, compared with the prior art, the invention has the following advantages: the concrete water reducing agent and the preparation method thereof provided by the invention have the advantages of simplicity and easiness in operation, low preparation cost, high preparation efficiency and high finished product qualification rate, and are suitable for continuous large-scale production. The concrete water reducing agent prepared by the preparation method has low mixing amount, high water reducing property, good plasticizing effect and no negative influence on the comprehensive performance of concrete, can obviously improve the fluidity and the working performance of the cement concrete of machine-made sand, improves the strength, the durability and the frost resistance of the concrete, and has good adaptability with the concrete; the rare earth metal organic framework material has a special atomic structure, a cavity structure and interface properties, can effectively change the crystal boundary energy of a cement hydration product, has the effects of refining the grain structure of the cement hydration product and improving the shape of crystal branches, ensures that the internal composition of concrete is more compact in a microscopic way, obviously increases the concrete strength in a macroscopic way, improves the durability of the concrete, and particularly is introduced in a metal organic framework way, so that the comprehensive performance of the concrete is improved; the introduced carboxyl modified N-vinyl carbazole/polyethylene glycol monoallyl ether/5-vinyl-1, 2, 4-oxadiazole-3-carboxylic acid ethyl ester copolymer and 3-aminopyrazine-2-carboxylic acid modified epoxy end group hyperbranched poly (amine-ester) and N-sulfo chitosan have synergistic effect, so that the flowability of cement concrete is effectively improved; the water-reducing agent can effectively disperse cement particles, further plays a role in water reduction, and the surface of the water-reducing agent is adsorbed with water molecules to form a water film which has a good lubricating effect, so that the flow resistance of concrete is reduced, and the fluidity of cement concrete of machine-made sand is improved.
Detailed Description
The concrete water reducing agent is characterized by being prepared from the following raw materials in parts by weight: 10-20 parts of carboxyl modified N-vinylcarbazole/polyethylene glycol monoallyl ether/5-vinyl-1, 2, 4-oxadiazole-3-ethyl carboxylate copolymer, 5-10 parts of 3-aminopyrazine-2-carboxylic acid modified epoxy-terminated hyperbranched poly (amine-ester), 2-4 parts of rare earth metal organic framework, 3-6 parts of N-sulfochitosan and 30-40 parts of water.
Preferably, the preparation method of the carboxyl modified N-vinylcarbazole/polyethylene glycol monoallyl ether/5-vinyl-1, 2, 4-oxadiazole-3-carboxylic acid ethyl ester copolymer comprises the following steps:
step S1, adding N-vinylcarbazole, polyethylene glycol monoallyl ether, 5-vinyl-1, 2, 4-oxadiazole-3-carboxylic acid ethyl ester and an initiator into a high-boiling-point solvent, stirring and reacting for 4-6 hours at 65-75 ℃ in a nitrogen or inert gas atmosphere, and then removing the solvent by rotary evaporation to obtain an N-vinylcarbazole/polyethylene glycol monoallyl ether/5-vinyl-1, 2, 4-oxadiazole-3-carboxylic acid ethyl ester copolymer;
step S2, adding the N-vinylcarbazole/polyethylene glycol monoallyl ether/5-vinyl-1, 2, 4-oxadiazole-3-carboxylic acid ethyl ester copolymer prepared in the step S1 into N-methylpyrrolidone, adding chloropropionic acid and a basic catalyst into the N-methylpyrrolidone, stirring the mixture at the temperature of 70-80 ℃ for reacting for 4-6 hours, and then removing the N-methylpyrrolidone by rotary evaporation; and dissolving the obtained crude product in water to form a solution, adding the solution into a dialysis bag, dialyzing in deionized water for 10-20 hours, and then performing rotary evaporation on the solution in the dialysis bag to remove water to obtain the product.
Preferably, the mass ratio of the N-vinylcarbazole, the polyethylene glycol monoallyl ether, the 5-vinyl-1, 2, 4-oxadiazole-3-carboxylic acid ethyl ester, the initiator and the high-boiling point solvent in the step S1 is 1:2 (0.1-0.4): 0.03-0.04): 12-20; the initiator is at least one of azobisisobutyronitrile and azobisisoheptonitrile; the high boiling point solvent is at least one of dimethyl sulfoxide, N-dimethylformamide, N-dimethylacetamide and N-methylpyrrolidone; in the step S2, the mass ratio of the N-vinylcarbazole/polyethylene glycol monoallyl ether/5-vinyl-1, 2, 4-oxadiazole-3-carboxylic acid ethyl ester copolymer, the N-methylpyrrolidone, the chloropropionic acid and the basic catalyst is 1 (5-10): 0.2-0.4): 0.4-0.7; the alkaline catalyst is at least one of sodium hydroxide, potassium hydroxide, sodium carbonate and potassium carbonate.
Further, the preparation method of the 3-aminopyrazine-2-carboxylic acid modified epoxy end group hyperbranched poly (amine-ester) comprises the following steps: adding 3-aminopyrazine-2-carboxylic acid and epoxy end group hyperbranched poly (amine-ester) into N, N-dimethylformamide, stirring and reacting for 6-8 hours at 80-90 ℃, and then removing the N, N-dimethylformamide by rotary evaporation to obtain 3-aminopyrazine-2-carboxylic acid modified epoxy end group hyperbranched poly (amine-ester); the mass ratio of the 3-aminopyrazine-2-carboxylic acid to the epoxy end group hyperbranched poly (amine-ester) to the N, N-dimethylformamide is 1 (4-7) to (20-30); the preparation method of the epoxy-terminated hyperbranched poly (amine-ester) is as follows: chinese patent application No. 200910067539.8, example 8.
Preferably, the preparation method of the rare earth metal organic framework is described in chinese patent application No. 201210245269.7, example 1; the preparation method of the N-sulfo chitosan is shown in the patent example 1 of Chinese invention with the application number of 03129053.1.
The invention also aims to provide a preparation method of the concrete water reducing agent, which is characterized by comprising the following steps: the raw materials are uniformly mixed according to the parts by weight, and are stirred and reacted for 4 to 7 hours at the temperature of between 45 and 60 ℃ to obtain the concrete water reducer.
Due to the application of the technical scheme, compared with the prior art, the invention has the following advantages: the concrete water reducing agent and the preparation method thereof provided by the invention have the advantages of simplicity and easiness in operation, low preparation cost, high preparation efficiency and high finished product qualification rate, and are suitable for continuous large-scale production. The concrete water reducing agent prepared by the preparation method has low mixing amount, high water reducing property, good plasticizing effect and no negative influence on the comprehensive performance of concrete, can obviously improve the fluidity and the working performance of the cement concrete of machine-made sand, improves the strength, the durability and the frost resistance of the concrete, and has good adaptability with the concrete; the rare earth metal organic framework material has a special atomic structure, a cavity structure and interface properties, can effectively change the crystal boundary energy of a cement hydration product, has the effects of refining the grain structure of the cement hydration product and improving the shape of crystal branches, ensures that the internal composition of concrete is more compact in a microscopic way, obviously increases the concrete strength in a macroscopic way, improves the durability of the concrete, and particularly is introduced in a metal organic framework way, so that the comprehensive performance of the concrete is improved; the introduced carboxyl modified N-vinyl carbazole/polyethylene glycol monoallyl ether/5-vinyl-1, 2, 4-oxadiazole-3-carboxylic acid ethyl ester copolymer and 3-aminopyrazine-2-carboxylic acid modified epoxy end group hyperbranched poly (amine-ester) and N-sulfo chitosan have synergistic effect, so that the flowability of cement concrete is effectively improved; the water-reducing agent can effectively disperse cement particles, further plays a role in water reduction, and the surface of the water-reducing agent is adsorbed with water molecules to form a water film which has a good lubricating effect, so that the flow resistance of concrete is reduced, and the fluidity of cement concrete of machine-made sand is improved.
The invention will be further described with reference to specific examples, but the scope of protection of the invention is not limited thereto:
example 1
Embodiment 1 provides a concrete water reducing agent, which is characterized by being prepared from the following raw materials in parts by weight: 10 parts of carboxyl modified N-vinyl carbazole/polyethylene glycol monoallyl ether/5-vinyl-1, 2, 4-oxadiazole-3-ethyl carboxylate copolymer, 5 parts of 3-aminopyrazine-2-carboxylic acid modified epoxy terminal hyperbranched poly (amine-ester), 2 parts of rare earth metal organic framework, 3 parts of N-sulfo chitosan and 30 parts of water.
The preparation method of the carboxyl modified N-vinylcarbazole/polyethylene glycol monoallyl ether/5-vinyl-1, 2, 4-oxadiazole-3-carboxylic acid ethyl ester copolymer comprises the following steps:
step S1, adding N-vinylcarbazole, polyethylene glycol monoallyl ether, 5-vinyl-1, 2, 4-oxadiazole-3-carboxylic acid ethyl ester and an initiator into a high-boiling-point solvent, stirring and reacting for 4 hours at 65 ℃ in a nitrogen or inert gas atmosphere, and then performing rotary evaporation to remove the solvent to obtain an N-vinylcarbazole/polyethylene glycol monoallyl ether/5-vinyl-1, 2, 4-oxadiazole-3-carboxylic acid ethyl ester copolymer;
step S2, adding the N-vinylcarbazole/polyethylene glycol monoallyl ether/5-vinyl-1, 2, 4-oxadiazole-3-carboxylic acid ethyl ester copolymer prepared in the step S1 into N-methylpyrrolidone, adding chloropropionic acid and a basic catalyst into the N-methylpyrrolidone, stirring the mixture at 70 ℃ for reacting for 4 hours, and then carrying out rotary evaporation to remove the N-methylpyrrolidone; and dissolving the obtained crude product in water to form a solution, adding the solution into a dialysis bag, dialyzing in deionized water for 10 hours, and then performing rotary evaporation on the solution in the dialysis bag to remove water to obtain the product.
In the step S1, the mass ratio of the N-vinylcarbazole, the polyethylene glycol monoallyl ether, the 5-vinyl-1, 2, 4-oxadiazole-3-carboxylic acid ethyl ester, the initiator and the high-boiling-point solvent is 1:2:0.1:0.03: 12.
The initiator is azobisisobutyronitrile; the high boiling point solvent is dimethyl sulfoxide.
In the step S2, the mass ratio of the N-vinylcarbazole/polyethylene glycol monoallyl ether/5-vinyl-1, 2, 4-oxadiazole-3-carboxylic acid ethyl ester copolymer, the N-methylpyrrolidone, the chloropropionic acid and the basic catalyst is 1:5:0.2: 0.4; the alkaline catalyst is sodium hydroxide.
The preparation method of the 3-aminopyrazine-2-carboxylic acid modified epoxy end group hyperbranched poly (amine-ester) comprises the following steps: adding 3-aminopyrazine-2-carboxylic acid and epoxy end group hyperbranched poly (amine-ester) into N, N-dimethylformamide, stirring and reacting for 6 hours at 80 ℃, and then performing rotary evaporation to remove the N, N-dimethylformamide to obtain 3-aminopyrazine-2-carboxylic acid modified epoxy end group hyperbranched poly (amine-ester); the mass ratio of the 3-aminopyrazine-2-carboxylic acid to the epoxy end group hyperbranched poly (amine-ester) to the N, N-dimethylformamide is 1:4: 20.
The preparation method of the concrete water reducing agent is characterized by comprising the following steps: the raw materials are uniformly mixed according to the parts by weight, and are stirred and reacted for 4 hours at the temperature of 45 ℃ to obtain the concrete water reducer.
Example 2
Embodiment 2 provides a concrete water reducing agent, the formula and preparation method of which are basically the same as those of embodiment 1, except that the concrete water reducing agent is prepared from the following raw materials in parts by weight: 13 parts of carboxyl modified N-vinyl carbazole/polyethylene glycol monoallyl ether/5-vinyl-1, 2, 4-oxadiazole-3-carboxylic acid ethyl ester copolymer, 6 parts of 3-aminopyrazine-2-carboxylic acid modified epoxy terminal hyperbranched poly (amine-ester), 2.5 parts of rare earth metal organic framework, 4 parts of N-sulfo chitosan and 32 parts of water.
Example 3
Embodiment 3 provides a concrete water reducing agent, the formula and preparation method of which are basically the same as those of embodiment 1, except that the concrete water reducing agent is prepared from the following raw materials in parts by weight: 15 parts of carboxyl modified N-vinyl carbazole/polyethylene glycol monoallyl ether/5-vinyl-1, 2, 4-oxadiazole-3-carboxylic acid ethyl ester copolymer, 8 parts of 3-aminopyrazine-2-carboxylic acid modified epoxy terminal hyperbranched poly (amine-ester), 3 parts of rare earth metal organic framework, 4.5 parts of N-sulfo chitosan and 35 parts of water.
Example 4
Embodiment 4 provides a concrete water reducing agent, which has a formula and a preparation method substantially the same as those of embodiment 1, except that the concrete water reducing agent is prepared from the following raw materials in parts by weight: 18 parts of carboxyl modified N-vinyl carbazole/polyethylene glycol monoallyl ether/5-vinyl-1, 2, 4-oxadiazole-3-carboxylic acid ethyl ester copolymer, 9 parts of 3-aminopyrazine-2-carboxylic acid modified epoxy terminal hyperbranched poly (amine-ester), 3.5 parts of rare earth metal organic framework, 5.5 parts of N-sulfo chitosan and 38 parts of water.
Example 5
Embodiment 5 provides a concrete water reducing agent, the formula and preparation method of which are basically the same as those of embodiment 1, except that the concrete water reducing agent is prepared from the following raw materials in parts by weight: 20 parts of carboxyl modified N-vinyl carbazole/polyethylene glycol monoallyl ether/5-vinyl-1, 2, 4-oxadiazole-3-carboxylic acid ethyl ester copolymer, 10 parts of 3-aminopyrazine-2-carboxylic acid modified epoxy terminal hyperbranched poly (amine-ester), 4 parts of rare earth metal organic framework, 6 parts of N-sulfo chitosan and 40 parts of water.
Comparative example 1
Comparative example 1 provides a concrete water reducing agent, the formulation and preparation method of which are substantially the same as in example 1, except that no carboxyl-modified N-vinylcarbazole/polyethylene glycol monoallyl ether/5-vinyl-1, 2, 4-oxadiazole-3-carboxylic acid ethyl ester copolymer was added.
Comparative example 2
Comparative example 2 provides a concrete water reducer having substantially the same formulation and preparation method as in example 1, except that 3-aminopyrazine-2-carboxylic acid modified epoxy terminated hyperbranched poly (amine-ester) was not added.
Comparative example 3
Comparative example 3 provides a concrete water reducing agent whose formulation and preparation method are substantially the same as those of example 1 except that N-sulfochitosan is not added.
Comparative example 4
Comparative example 4 provides a concrete water-reducing agent whose formulation and preparation method are substantially the same as those of example 1 except that no rare earth metal organic framework is added.
The concrete water reducing agents described in examples 1 to 5 and comparative examples 1 to 4 were subjected to performance tests, and the test results are shown in Table 1. The performance test method is carried out by referring to JG/T223-2007, and the mixing amount of the water reducing agent is 0.1%.
TABLE 1
| Test items | Water reduction rate | Compressive strength ratio of 7 days | Compressive strength ratio of 28 days | Corrosion to reinforcing steel bar |
| Unit of | ％ | ％ | ％ | - |
| Example 1 | 33 | 136 | 130 | Passivation of |
| Example 2 | 35 | 138 | 134 | Passivation of |
| Example 3 | 36 | 141 | 137 | Passivation of |
| Example 4 | 38 | 144 | 140 | Passivation of |
| Example 5 | 40 | 145 | 143 | Passivation of |
| Comparative example 1 | 25 | 123 | 112 | Passivation of |
| Comparative example 2 | 23 | 125 | 115 | Passivation of |
| Comparative example 3 | 23 | 123 | 111 | Passivation of |
| Comparative example 4 | 28 | 120 | 110 | Passivation of |
As can be seen from Table 1, the concrete water reducing agent disclosed in the embodiment of the invention has better water reducing effect, higher compressive strength and no corrosion effect on reinforcing steel bars compared with the concrete water reducing agent in the comparative example.
The above embodiments are merely illustrative of the technical ideas and features of the present invention, and the purpose thereof is to enable those skilled in the art to understand the contents of the present invention and implement the present invention, and not to limit the protection scope of the present invention. All equivalent changes and modifications made according to the spirit of the present invention should be covered within the protection scope of the present invention.
Claims (9)
1. The concrete water reducing agent is characterized by being prepared from the following raw materials in parts by weight: 10-20 parts of carboxyl modified N-vinylcarbazole/polyethylene glycol monoallyl ether/5-vinyl-1, 2, 4-oxadiazole-3-ethyl carboxylate copolymer, 5-10 parts of 3-aminopyrazine-2-carboxylic acid modified epoxy-terminated hyperbranched poly (amine-ester), 2-4 parts of rare earth metal organic framework, 3-6 parts of N-sulfochitosan and 30-40 parts of water.
2. The concrete water reducer according to claim 1, wherein the preparation method of the carboxyl-modified N-vinylcarbazole/polyethylene glycol monoallyl ether/5-vinyl-1, 2, 4-oxadiazole-3-carboxylic acid ethyl ester copolymer comprises the following steps:
step S1, adding N-vinylcarbazole, polyethylene glycol monoallyl ether, 5-vinyl-1, 2, 4-oxadiazole-3-carboxylic acid ethyl ester and an initiator into a high-boiling-point solvent, stirring and reacting for 4-6 hours at 65-75 ℃ in a nitrogen or inert gas atmosphere, and then removing the solvent by rotary evaporation to obtain an N-vinylcarbazole/polyethylene glycol monoallyl ether/5-vinyl-1, 2, 4-oxadiazole-3-carboxylic acid ethyl ester copolymer;
step S2, adding the N-vinylcarbazole/polyethylene glycol monoallyl ether/5-vinyl-1, 2, 4-oxadiazole-3-carboxylic acid ethyl ester copolymer prepared in the step S1 into N-methylpyrrolidone, adding chloropropionic acid and a basic catalyst into the N-methylpyrrolidone, stirring the mixture at the temperature of 70-80 ℃ for reacting for 4-6 hours, and then removing the N-methylpyrrolidone by rotary evaporation; and dissolving the obtained crude product in water to form a solution, adding the solution into a dialysis bag, dialyzing in deionized water for 10-20 hours, and then performing rotary evaporation on the solution in the dialysis bag to remove water to obtain the product.
3. The water reducing agent for concrete according to claim 2, wherein in step S1, the mass ratio of the N-vinylcarbazole, the polyethylene glycol monoallyl ether, the ethyl 5-vinyl-1, 2, 4-oxadiazole-3-carboxylate, the initiator and the high-boiling point solvent is 1:2 (0.1-0.4): 0.03-0.04): 12-20.
4. The concrete water reducer according to claim 2, wherein the initiator is at least one of azobisisobutyronitrile and azobisisoheptonitrile; the high boiling point solvent is at least one of dimethyl sulfoxide, N-dimethylformamide, N-dimethylacetamide and N-methylpyrrolidone.
5. The water reducing agent for concrete according to claim 2, wherein in step S2, the mass ratio of the N-vinylcarbazole/polyethylene glycol monoallyl ether/5-vinyl-1, 2, 4-oxadiazole-3-carboxylic acid ethyl ester copolymer, the N-methylpyrrolidone, the chloropropionic acid and the basic catalyst is 1 (5-10): (0.2-0.4): (0.4-0.7).
6. The concrete water reducer of claim 2, wherein the basic catalyst is at least one of sodium hydroxide, potassium hydroxide, sodium carbonate and potassium carbonate.
7. The concrete water reducer according to claim 1, wherein the preparation method of the 3-aminopyrazine-2-carboxylic acid modified epoxy-terminated hyperbranched poly (amine-ester) comprises the following steps: adding 3-aminopyrazine-2-carboxylic acid and epoxy end group hyperbranched poly (amine-ester) into N, N-dimethylformamide, stirring and reacting for 6-8 hours at 80-90 ℃, and then removing the N, N-dimethylformamide by rotary evaporation to obtain the 3-aminopyrazine-2-carboxylic acid modified epoxy end group hyperbranched poly (amine-ester).
8. The concrete water reducer according to claim 7, wherein the mass ratio of the 3-aminopyrazine-2-carboxylic acid to the epoxy-terminated hyperbranched poly (amine-ester) to the N, N-dimethylformamide is 1 (4-7) to (20-30).
9. The concrete water reducer according to any one of claims 1 to 8, wherein the preparation method of the concrete water reducer comprises the following steps: the raw materials are uniformly mixed according to the parts by weight, and are stirred and reacted for 4 to 7 hours at the temperature of between 45 and 60 ℃ to obtain the concrete water reducer.
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