CN111019063A - High-performance polycarboxylic acid water reducer with high water reduction and low collapse loss and preparation method thereof - Google Patents
High-performance polycarboxylic acid water reducer with high water reduction and low collapse loss and preparation method thereof Download PDFInfo
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- 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
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- 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
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- C04B24/24—Macromolecular compounds
- C04B24/26—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- C04B24/2664—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of ethylenically unsaturated dicarboxylic acid polymers, e.g. maleic anhydride copolymers
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- C04B2103/00—Function or property of ingredients for mortars, concrete or artificial stone
- C04B2103/30—Water reducers, plasticisers, air-entrainers, flow improvers
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Abstract
The high-performance polycarboxylic acid water reducing agent with high water reduction and low collapse loss is prepared from a high-molecular-weight methallyl alcohol polyoxyethylene ether comonomer, a fully esterified isomeric ester, an unsaturated carboxylic acid comonomer, a reactive initiator, an oxidant, liquid alkali and water. The water reducer can integrate the advantages of two water reducers, namely an ester water reducer and an ether water reducer, and mutually make up the respective defects. The completely esterified isomeric ester has high reactivity, can promote the reaction of a high molecular weight methallyl alcohol polyoxyethylene ether comonomer and an unsaturated carboxylic acid comonomer, has a synergistic effect, has an adjustable hydrophobic chain segment, can adjust the molecular weight and the hydrophilic-hydrophobic proportion according to different ground materials, enables the prepared water reducing agent to have wider adaptability, and can ensure good workability and collapse protection. Meanwhile, the polycarboxylate superplasticizer prepared by utilizing the raw materials in the invention has strong steric hindrance effect, so that cement particles are more dispersed to obtain better water reducing effect.
Description
Technical Field
The invention relates to the technical field of concrete admixtures, in particular to a polycarboxylic acid high-performance water reducing agent with high water reducing capacity and low collapse loss and a preparation method thereof.
Background
As one of common building base materials, concrete is widely used in more and more fields along with the continuous development and improvement of concrete technology, but simultaneously, the concrete also puts higher and higher requirements on the performance of the concrete. The concrete water reducing agent can reduce the cement consumption of concrete and improve the utilization rate of industrial waste residues, and the addition of the water reducing agent into the concrete is the simplest, most effective and most economical technical means for improving the strength, the working performance and the durability of the concrete and is also the core technology of modern concrete preparation.
Along with the large-scale development of infrastructure engineering construction in China, the polycarboxylic acid high-performance water reducing agent is widely used. The polycarboxylic acid high-performance water reducing agent can be divided into an ester water reducing agent and an ether water reducing agent according to the connection mode of a main chain and a branched chain. The ester water reducing agent has better adaptability to cement, has the advantages of low sensitivity to doping amount and materials, better workability and wrapping property of concrete and the like, but has harsh synthesis conditions, higher cost, complex production process and higher requirement on product quality control; the ether water reducing agent has high water reducing rate, low price and simple production process, but the too high water reducing rate can easily cause the segregation and bleeding of the medium and low grade concrete, the situations of poor workability and wrapping property occur, the mixing amount is sensitive, and the adaptability difference of various cements is large. In actual engineering, the use effect of the polycarboxylate superplasticizer is directly influenced by respective defects of the ester or ether polycarboxylate superplasticizer.
Therefore, aiming at the defects in the prior art, it is necessary to provide a high-performance polycarboxylic acid water reducing agent with high water reduction and low collapse loss, which has the common advantages of an ester water reducing agent and an ether water reducing agent, so as to overcome the defects in the prior art.
Disclosure of Invention
The invention aims to avoid the defects of the prior art and provide the polycarboxylic acid high-performance water reducing agent with high water reducing rate and low collapse loss, which has the characteristics of wide adaptability, excellent workability, high water reducing rate and low collapse loss.
The above object of the present invention is achieved by the following technical measures.
The high-performance polycarboxylic acid water reducing agent with high water reducing rate and low collapse loss is prepared from a high-molecular-weight methallyl alcohol polyoxyethylene ether comonomer, a fully esterified isomeric ester, an unsaturated carboxylic acid comonomer, a reactive initiator, an oxidant, liquid alkali and water.
Preferably, the proportion of the synthetic raw materials is as follows by weight:
preferably, the proportion of the synthetic raw materials is as follows by weight:
preferably, the proportion of the synthetic raw materials is as follows by weight:
preferably, the proportion of the synthetic raw materials is as follows by weight:
preferably, the proportion of the synthetic raw materials is as follows by weight:
preferably, the high molecular weight methallyl alcohol polyoxyethylene ether comonomer is one or more of oxk 501, oxk 608, Guangzhou Bofeng TPEG2400 or Jiangsu Haian TPEG (F-108);
the completely esterified isomeric ester is a completely esterified isomeric Craine ester, and the molecular weight is 1000-3000;
the unsaturated carboxylic acid comonomer is one or a combination of more of methacrylic acid, acrylic acid and maleic anhydride;
the reactive initiator is a mixture of an azo compound and a reducing agent, and the azo compound is one or a combination of two of azodiisobutyronitrile or azodiisoheptanonitrile; the reducing agent is one or more of sodium sulfite, L-ascorbic acid, sodium bisulfite, ferrous sulfate and sodium formaldehyde sulfoxylate;
the oxidant is peroxide, and the peroxide is one or a combination of hydrogen peroxide, ammonium persulfate, potassium persulfate and sodium persulfate.
The high-performance polycarboxylic acid water reducing agent with high water reduction and low collapse loss is prepared from a high-molecular-weight methallyl alcohol polyoxyethylene ether comonomer, a fully esterified isomeric ester, an unsaturated carboxylic acid comonomer, a reactive initiator, an oxidant, liquid alkali and water. The water reducer can integrate the advantages of two water reducers, namely an ester water reducer and an ether water reducer, and mutually make up the respective defects. The completely esterified isomeric ester has high reactivity, can promote the reaction of a high molecular weight methallyl alcohol polyoxyethylene ether comonomer and an unsaturated carboxylic acid comonomer, has a synergistic effect, has an adjustable hydrophobic chain segment, can adjust the molecular weight and the hydrophilic-hydrophobic proportion according to different ground materials, enables the prepared water reducing agent to have wider adaptability, and can ensure good workability and collapse protection. Meanwhile, the polycarboxylate superplasticizer prepared by utilizing the raw materials in the invention has strong steric hindrance effect, so that cement particles are more dispersed to obtain better water reducing effect.
The invention also aims to avoid the defects of the prior art and provide a preparation method of the low-collapse-loss polycarboxylic acid high-performance water reducing agent, which can be used for preparing the water reducing agent with wide adaptability, excellent workability, high water reducing rate and low collapse loss.
The above object of the present invention is achieved by the following technical measures.
The preparation method of the polycarboxylic acid high-performance water reducer with high water reduction and low collapse loss comprises the following steps:
(1) adding a high molecular weight methallyl alcohol polyoxyethylene ether comonomer and a reactive initiator into a four-neck flask provided with a stirrer and a thermometer, adding water, stirring for 5-10 min, and then simultaneously dropwise adding a material I solution and a material II solution;
(2) after the material I solution and the material II solution are dripped, preserving the heat for 0.5 to 1.5 hours at the temperature of between 35 and 45 ℃;
(3 after the reaction is finished, adding alkali liquor to neutralize the pH value of the solution to 6-7 when the temperature of the solution is cooled to 30 ℃.
Preferably, the material I solution is prepared by uniformly stirring unsaturated carboxylic acid comonomer, completely esterified isomeric ester and water, and the material II solution is prepared by uniformly stirring peroxide and water.
Preferably, the dripping duration of the material I solution is 2.5 to 3.5 hours, and the dripping duration of the material II solution is 3 to 4 hours.
The invention relates to a preparation method of a polycarboxylic acid high-performance water reducing agent with high water reduction and low collapse loss, which comprises the following steps: (1) adding a high molecular weight methallyl alcohol polyoxyethylene ether comonomer and a reactive initiator into a four-neck flask provided with a stirrer and a thermometer, adding water, stirring for 5-10 min, and then simultaneously dropwise adding a material I solution and a material II solution; (2) after the material I solution and the material II solution are dripped, preserving the heat for 0.5 to 1.5 hours at the temperature of between 35 and 45 ℃; (3 after the reaction is finished, adding alkali liquor to neutralize the pH value of the solution to 6-7 when the temperature of the solution is cooled to 30 ℃, the method is simple in process and high in preparation purity, and the prepared polycarboxylic acid water reducing agent is excellent in performance, has the characteristics of wide adaptability, excellent workability, high water reducing rate and low collapse loss, and lays a good technical foundation for wide application and industrial development of concrete.
Detailed Description
The invention is further illustrated by the following examples.
Example 1.
A polycarboxylic acid high-performance water reducing agent with high water reducing performance and low collapse loss is prepared from high-molecular-weight methallyl alcohol polyoxyethylene ether comonomer, fully esterified isomeric ester, unsaturated carboxylic acid comonomer, reactive initiator, oxidant, liquid alkali and water. Compared with ether monomers, the completely esterified isomeric ester has higher reactivity, and can promote the reaction of a high molecular weight methallyl alcohol polyoxyethylene ether comonomer and an unsaturated carboxylic acid comonomer, so that the synergistic interaction effect is achieved.
In the embodiment, the ratio of the synthetic raw materials is as follows by weight:
in the embodiment, the high molecular weight methallyl alcohol polyoxyethylene ether comonomer is one or more of oxk 501, oxk 608, Guangzhou Bofeng TPEG2400 or Jiangsu Hai' an TPEG (F-108). The methallyl alcohol polyoxyethylene ether is easy to dissolve in water, so that the polycarboxylate superplasticizer has high-efficiency particle dispersing performance and retention capacity. The completely esterified isomeric ester is a completely esterified isomeric ester of Craine, the molecular weight is 1000-3000, and the more the molecular weight is, the more obvious the reaction promotion effect on other macromonomers in the reaction system is. The unsaturated carboxylic acid comonomer is one or more of methacrylic acid, acrylic acid and maleic anhydride.
The reactive initiator is a mixture of an azo compound and a reducing agent, and the azo compound is one or the combination of two of azodiisobutyronitrile or azodiisoheptanonitrile. The azo compound has stable reaction, is a first-order reaction, has no side reaction, is well controlled, and has molecules which are easy to generate splitting reaction to form molecules with high activation energy, so the azo compound is selected as an initiator, and the reducing agent is one or more of sodium sulfite, L-ascorbic acid, sodium bisulfite, ferrous sulfate and formaldehyde sodium sulfoxylate. The oxidant is peroxide, and the peroxide is one or a combination of hydrogen peroxide, ammonium persulfate, potassium persulfate and sodium persulfate. The redox reaction of the oxidizing agent and the reducing agent provides heat for the reaction of each molecular monomer.
The preparation method of the polycarboxylic acid high-performance water reducer with high water reduction and low collapse loss comprises the following steps: (1) adding a high molecular weight methallyl alcohol polyoxyethylene ether comonomer and a reactive initiator into a four-neck flask provided with a stirrer and a thermometer, adding water, stirring for 5min, and then simultaneously dropwise adding a material I solution and a material II solution; (2) after the material I solution and the material II solution are dripped, preserving the heat for 0.5h within the temperature range of 35 ℃; (3) and after the reaction is finished, cooling the solution to 30 ℃, and adding alkali liquor to neutralize the pH value of the solution to 6-7.
In this example, the material I solution is a solution prepared by uniformly stirring an unsaturated carboxylic acid comonomer, a completely esterified isomeric ester and water, and the material II solution is a solution prepared by uniformly stirring a peroxide and water. The continuous dripping time of the material I solution is 2.5 hours, and the continuous dripping time of the material II solution is 3 hours. And respectively dripping the material I solution and the material II solution into a four-neck flask, which is beneficial to reducing impurities in the reaction process.
The high-performance polycarboxylic acid water reducing agent with high water reduction and low collapse loss can integrate the advantages of an ester water reducing agent and an ether water reducing agent, has the characteristics of wide adaptability, excellent workability, high water reduction rate and low collapse loss rate, is simple in preparation method process, and lays a good foundation for wide application of concrete and development of the concrete industry.
Example 2.
The other characteristics of the polycarboxylic acid high-performance water reducing agent with high water reduction and low collapse loss are the same as those of the embodiment 1, except that: the synthetic raw materials comprise the following components in parts by weight:
the polycarboxylic acid high-performance water reducing agent with high water reduction and low collapse loss is prepared by the following steps: (1) adding a high molecular weight methallyl alcohol polyoxyethylene ether comonomer and a reactive initiator into a four-neck flask provided with a stirrer and a thermometer, adding water, stirring for 6min, and then simultaneously dropwise adding a material I solution and a material II solution; (2) after the material I solution and the material II solution are dripped, preserving the heat for 0.7h within the temperature range of 37 ℃; (3) and after the reaction is finished, cooling the solution to 30 ℃, and adding alkali liquor to neutralize the pH value of the solution to 6-7.
In this example, the material I solution is a solution prepared by uniformly stirring an unsaturated carboxylic acid comonomer, a completely esterified isomeric ester and water, and the material II solution is a solution prepared by uniformly stirring a peroxide and water. The continuous dripping time of the material I solution is 2.7 hours, and the continuous dripping time of the material II solution is 3.2 hours. And respectively dripping the material I solution and the material II solution into a four-neck flask, which is beneficial to reducing impurities in the reaction process.
In order to test the performance of the polycarboxylic acid high-performance water reducing agent with high water reduction and low collapse loss, the water reducing agent is tested according to the relevant regulations of national standard GB 8076-.
TABLE 1 concrete mix proportion (kg/m3)
In addition, in this example, a common polycarboxylate superplasticizer a was selected as comparative example 1 to perform the same test on the concrete as the water reducer of the present invention, and the preparation method of the common polycarboxylate superplasticizer is as follows: putting 340 parts of polyprenyl polyoxyethylene ether with the molecular weight of 2400 into a four-neck flask provided with a stirrer and a thermometer, adding 230 parts of water, starting stirring, heating to 50 ℃, after monomers in the flask are completely dissolved, adding 2.0 parts of hydrogen peroxide, stirring for 10min, then simultaneously dropwise adding a material I solution and a material II solution, adding a solution prepared by uniformly stirring 31 parts of acrylic acid and 100 parts of water into the material I solution, dropwise adding for 3h, adding a solution prepared by uniformly stirring 0.9 part of L-ascorbic acid, 1.1 parts of mercaptoethanol and 110 parts of water into the material II solution, dropwise adding for 3.5h, continuously preserving heat at 50 ℃ for 1h after dropwise adding, cooling 50 parts of water to about 30 ℃ after the reaction is finished, adding alkali to neutralize to the pH value of about 6-7, and preparing the common polycarboxylic acid water reducer A.
The concrete performance ratio of the concrete satisfying the concrete mixing ratio is shown in table 2 after the concrete satisfying the synthetic raw material ratio of the embodiment is added with the polycarboxylic acid high-performance water reducing agent with high water reduction and low collapse loss or the common polycarboxylic acid water reducing agent A.
Table 2 comparison of concrete Properties Using the Water reducing agent of this example or the ordinary polycarboxylic acid Water reducing agent A
And (3) analyzing an experimental result: under the condition of basically consistent initial slump and expansion of concrete used in control experiments, compared with the common polycarboxylate superplasticizer A, the high-performance polycarboxylate superplasticizer A prepared by the method has the advantages that the mixing amount of the high-performance polycarboxylate superplasticizer A with high water reduction and low collapse loss is obviously less, and the high-performance polycarboxylate superplasticizer shows excellent concrete water reduction rate. In addition, as can be clearly seen from the table, after the same time, the slump and the expansion degree of the common polycarboxylic acid water reducing agent A are reduced by far more than that of the water reducing agent of the invention, and the reduction speed is far more than that of the invention, so that the polycarboxylic acid high-performance water reducing agent with high water reducing and low collapse loss of the invention is proved to have excellent collapse protection performance and good workability. We can also see from the table that after the same time, the compressive strength of the concrete using the high water-reducing and low-collapse-loss polycarboxylate high-performance water reducer of the invention is higher than that of the concrete using the common polycarboxylate water reducer A, and the concrete shows good comprehensive performance, and the superiority of the high water-reducing and low-collapse-loss polycarboxylate high-performance water reducer compared with the common polycarboxylate water reducer is proved again.
In conclusion, the polycarboxylic acid high-performance water reducing agent with high water reducing and low collapse loss can reduce the slump and the expansion degree of concrete, has excellent workability and high water reducing rate, and can completely meet the requirement on the strength of the concrete, the concrete has good state and good wrapping property, and the 28-day compressive strength exceeds 34 MPa. Meanwhile, the preparation method is simple in process, and the prepared raw materials are high in purity, so that a good foundation is laid for the wide use of concrete and the development of the concrete industry.
Example 3.
A polycarboxylic acid high-performance water reducing agent with high water reducing and low collapse loss is the same as the polycarboxylic acid high-performance water reducing agent in example 2 with the following other characteristics: the synthetic raw materials comprise the following components in parts by weight:
the preparation method of the polycarboxylic acid high-performance water reducer with high water reduction and low collapse loss comprises the following steps: (1) adding a high molecular weight methallyl alcohol polyoxyethylene ether comonomer and a reactive initiator into a four-neck flask provided with a stirrer and a thermometer, adding water, stirring for 7min, and then simultaneously dropwise adding a material I solution and a material II solution; (2) after the material I solution and the material II solution are dripped, preserving the heat for 0.9h within the temperature range of 37 ℃; (3) and after the reaction is finished, cooling the solution to 30 ℃, and adding alkali liquor to neutralize the pH value of the solution to 6-7.
In this example, the material I solution is a solution prepared by uniformly stirring an unsaturated carboxylic acid comonomer, a completely esterified isomeric ester and water, and the material II solution is a solution prepared by uniformly stirring a peroxide and water. The continuous dripping time of the material I solution is 2.9 hours, and the continuous dripping time of the material II solution is 3.4 hours. And respectively dripping the material I solution and the material II solution into a four-neck flask, which is beneficial to reducing impurities in the reaction process.
Similarly, the polycarboxylic acid high-performance water reducing agent with high water reduction and low collapse loss of the embodiment is tested, the common polycarboxylic acid water reducing agent A in the comparative example 1 is selected as a comparative test object, the mixing proportion of the concrete selected in the test is the same as that in the embodiment 2, and then the test is carried out according to the relevant regulations of the national standard GB 8076-. The concrete performance ratio of the polycarboxylic acid high-performance water reducing agent with high water reduction and low collapse loss or the common polycarboxylic acid water reducing agent A prepared according to the raw material ratio in the embodiment is shown in Table 3.
Table 3 comparison of concrete Properties Using the Water reducer of this example with the ordinary polycarboxylic acid Water reducer A
And (3) analyzing an experimental result: under the condition of basically consistent initial slump and expansion of concrete used in control experiments, compared with the common polycarboxylate superplasticizer A, the high-performance polycarboxylate superplasticizer A prepared by the method has the advantages that the mixing amount of the high-performance polycarboxylate superplasticizer A with high water reduction and low collapse loss is obviously less, and the high-performance polycarboxylate superplasticizer shows excellent concrete water reduction rate. In addition, as can be clearly seen from the table, after the same time, the slump and the expansion degree of the common polycarboxylic acid water reducing agent A are reduced by far more than that of the water reducing agent of the invention, and the reduction speed is far more than that of the invention, so that the polycarboxylic acid high-performance water reducing agent with high water reducing and low collapse loss of the invention is proved to have excellent collapse protection performance and good workability. We can also see from the table that after the same time, the compressive strength of the concrete using the high water-reducing and low-collapse-loss polycarboxylate high-performance water reducer of the invention is higher than that of the concrete using the common polycarboxylate water reducer A, and the concrete shows good comprehensive performance, and the superiority of the high water-reducing and low-collapse-loss polycarboxylate high-performance water reducer compared with the common polycarboxylate water reducer is proved again.
In conclusion, the polycarboxylic acid high-performance water reducing agent with high water reduction and low collapse loss can reduce the slump and the expansion degree of concrete, has excellent workability and high water reduction rate, and can ensure that the concrete state is good over time, the 28-day compressive strength exceeds 35MPa, and the concrete strength requirement is completely met. Meanwhile, the preparation method is simple in process, and the prepared raw materials are high in purity, so that a good foundation is laid for the wide use of concrete and the development of the concrete industry.
Example 4.
A polycarboxylic acid high-performance water reducing agent with high water reducing and low collapse loss is the same as the polycarboxylic acid high-performance water reducing agent in example 2 with the following other characteristics: the synthetic raw materials comprise the following components in parts by weight:
the preparation method of the polycarboxylic acid high-performance water reducer with high water reduction and low collapse loss comprises the following steps: (1) adding a high molecular weight methallyl alcohol polyoxyethylene ether comonomer and a reactive initiator into a four-neck flask provided with a stirrer and a thermometer, adding water, stirring for 10min, and then simultaneously dropwise adding a material I solution and a material II solution; (2) after the material I solution and the material II solution are dripped, preserving the heat for 1h within the temperature range of 40 ℃; (3) and after the reaction is finished, cooling the solution to 30 ℃, and adding alkali liquor to neutralize the pH value of the solution to 6-7.
In this example, the material I solution is a solution prepared by uniformly stirring an unsaturated carboxylic acid comonomer, a completely esterified isomeric ester and water, and the material II solution is a solution prepared by uniformly stirring a peroxide and water. The continuous dripping time of the material I solution is 3 hours, and the continuous dripping time of the material II solution is 3.5 hours. And respectively dripping the material I solution and the material II solution into a four-neck flask, which is beneficial to reducing impurities in the reaction process.
Similarly, the polycarboxylic acid high-performance water reducing agent with high water reduction and low collapse loss of the embodiment is tested, the concrete mixing proportion selected in the test is the same as that in the embodiment 2, and then the test is carried out according to the relevant regulations of the national standard GB 8076-.
In addition, in this example, a common polycarboxylate superplasticizer B was selected as comparative example 2 to perform the same test on the concrete as the water reducer of the present invention, and the preparation method of the common polycarboxylate superplasticizer is as follows: putting 340 parts of polyprenyl polyoxyethylene ether with the molecular weight of 2400 into a four-neck flask provided with a stirrer and a thermometer, adding 230 parts of water, starting stirring, heating to 50 ℃, after monomers in the flask are completely dissolved, putting 2.0 parts of hydrogen peroxide, stirring for 10min, then simultaneously dropwise adding a material I solution and a material II solution, adding a solution prepared by uniformly stirring 31 parts of acrylic acid and 100 parts of water into the material I solution, dropwise adding for 3h, adding a solution prepared by uniformly stirring 0.9 part of L-ascorbic acid, 1.1 parts of mercaptoethanol and 110 parts of water into the material II solution, dropwise adding for 3.5h, continuously preserving heat at 50 ℃ for 1h after dropwise adding, cooling 50 parts of water to about 30 ℃ after the reaction is finished, adding alkali to neutralize to the pH value of about 6-7, and preparing the common polycarboxylic acid water reducer B.
The concrete performance ratio of the concrete satisfying the concrete mixing ratio is shown in table 4 after the concrete satisfying the synthetic raw material ratio of the embodiment is added with the polycarboxylic acid high-performance water reducing agent with high water reduction and low collapse loss or the common polycarboxylic acid water reducing agent B.
Table 4 comparison of concrete Properties Using the Water reducing agent of this example with the ordinary polycarboxylic acid Water reducing agent B
And (3) analyzing an experimental result: under the condition of basically consistent initial slump and expansion of concrete used in control experiments, compared with a common polycarboxylic acid water reducing agent B, the high-performance polycarboxylic acid water reducing agent with high water reduction and low collapse loss prepared by the invention is added in a smaller amount, and the water reducing agent shows excellent concrete water reduction rate. In addition, as can be clearly seen from the table, after the same time, the slump and the expansion degree of the common polycarboxylic acid water reducing agent A are reduced by far more than that of the water reducing agent of the invention, and the reduction speed is far more than that of the invention, so that the polycarboxylic acid high-performance water reducing agent with high water reducing and low collapse loss of the invention is proved to have excellent collapse protection performance and good workability. We can also see from the table that after the same time, the compressive strength of the concrete using the high water-reducing and low-collapse-loss polycarboxylate high-performance water reducer of the invention is higher than that of the concrete using the common polycarboxylate water reducer B, and the concrete shows good comprehensive performance, and the superiority of the high water-reducing and low-collapse-loss polycarboxylate high-performance water reducer compared with the common polycarboxylate water reducer is proved again.
In conclusion, the polycarboxylic acid high-performance water reducing agent with high water reduction and low collapse loss can reduce the slump and the expansion degree of concrete, has excellent workability and high water reduction rate, and can ensure that the concrete has good state with the 28-day compressive strength exceeding 34MPa and completely meet the requirement on the strength of the concrete. Meanwhile, the preparation method is simple in process, and the prepared raw materials are high in purity, so that a good foundation is laid for the wide use of concrete and the development of the concrete industry.
Example 5.
A polycarboxylic acid high-performance water reducing agent with high water reduction and low collapse loss is the same as the polycarboxylic acid high-performance water reducing agent in example 3 with the following other characteristics:
the preparation method of the polycarboxylic acid high-performance water reducer with high water reduction and low collapse loss comprises the following steps: (1) adding a high molecular weight methallyl alcohol polyoxyethylene ether comonomer and a reactive initiator into a four-neck flask provided with a stirrer and a thermometer, adding water, stirring for 10min, and then simultaneously dropwise adding a material I solution and a material II solution; (2) after the material I solution and the material II solution are dripped, preserving the heat for 1.5h within the temperature range of 45 ℃; (3) and after the reaction is finished, cooling the solution to 30 ℃, and adding alkali liquor to neutralize the pH value of the solution to 6-7.
In this example, the material I solution is a solution prepared by uniformly stirring an unsaturated carboxylic acid comonomer, a completely esterified isomeric ester and water, and the material II solution is a solution prepared by uniformly stirring a peroxide and water. The continuous dripping time of the material I solution is 3.5 hours, and the continuous dripping time of the material II solution is 4 hours. And respectively dripping the material I solution and the material II solution into a four-neck flask, which is beneficial to reducing impurities in the reaction process.
Similarly, the polycarboxylic acid high-performance water reducing agent with high water reduction and low collapse loss of the embodiment is tested, the common polycarboxylic acid water reducing agent B of the comparative example 2 is selected as a comparative test object, the mixing proportion of the concrete selected in the test is the same as that in the embodiment 2, and then the test is carried out according to the relevant regulations of national standard GB 8076-. The concrete performance ratio of the polycarboxylic acid high-performance water reducing agent with high water reduction and low collapse loss or the common polycarboxylic acid water reducing agent A prepared according to the raw material ratio in the embodiment is shown in Table 5.
Table 5 comparison of concrete Properties Using the Water reducer of this example with the ordinary polycarboxylic acid Water reducer B
And (3) analyzing an experimental result: under the condition of basically consistent initial slump and expansion of concrete used in control experiments, compared with a common polycarboxylic acid water reducing agent B, the high-performance polycarboxylic acid water reducing agent with high water reduction and low collapse loss prepared by the invention is added in a smaller amount, and the water reducing agent shows excellent concrete water reduction rate. In addition, as can be clearly seen from the table, after the same time, the slump and the expansion degree of the common polycarboxylic acid water reducing agent A are reduced by far more than that of the water reducing agent of the invention, and the reduction speed is far more than that of the invention, so that the polycarboxylic acid high-performance water reducing agent with high water reducing and low collapse loss of the invention is proved to have excellent collapse protection performance and good workability. We can also see from the table that after the same time, the compressive strength of the concrete using the high water-reducing and low-collapse-loss polycarboxylate high-performance water reducer of the invention is higher than that of the concrete using the common polycarboxylate water reducer B, and the concrete shows good comprehensive performance, and the superiority of the high water-reducing and low-collapse-loss polycarboxylate high-performance water reducer compared with the common polycarboxylate water reducer is proved again.
In conclusion, the polycarboxylic acid high-performance water reducing agent with high water reduction and low collapse loss can reduce the slump and the expansion degree of concrete, has excellent workability and high water reduction rate, and can ensure that the concrete state is good over time, the 28-day compressive strength exceeds 35MPa, and the concrete strength requirement is completely met. Meanwhile, the preparation method is simple in process, and the prepared raw materials are high in purity, so that a good foundation is laid for the wide use of concrete and the development of the concrete industry.
Finally, it should be noted that the above embodiments are only used for illustrating the technical solutions of the present invention and not for limiting the protection scope of the present invention, and although the present invention is described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that modifications or equivalent substitutions can be made on the technical solutions of the present invention without departing from the spirit and scope of the technical solutions of the present invention.
Claims (10)
1. The polycarboxylic acid high-performance water reducing agent with high water reducing performance and low collapse loss is characterized in that synthetic raw materials comprise a high-molecular-weight methallyl alcohol polyoxyethylene ether comonomer, a fully esterified isomeric ester, an unsaturated carboxylic acid comonomer, a reactive initiator, an oxidant, liquid alkali and water.
2. The high water reducing and low collapse loss polycarboxylic acid high performance water reducing agent according to claim 1, which is characterized in that the ratio of the synthetic raw materials is as follows by weight:
3. the high water reducing and low collapse loss polycarboxylic acid high performance water reducing agent according to claim 1, which is characterized in that the ratio of the synthetic raw materials is as follows by weight:
4. the high water reducing and low collapse loss polycarboxylic acid high performance water reducing agent according to claim 1, which is characterized in that the ratio of the synthetic raw materials is as follows by weight:
5. the high water reducing and low collapse loss polycarboxylic acid high performance water reducing agent according to claim 1, which is characterized in that the ratio of the synthetic raw materials is as follows by weight:
6. the high water reducing and low collapse loss polycarboxylic acid high performance water reducing agent according to claim 1, which is characterized in that the ratio of the synthetic raw materials is as follows by weight:
7. the high water reduction, low collapse loss polycarboxylic acid high performance water reducer according to any one of claims 1 to 6, characterized in that the high molecular weight methallyl alcohol polyoxyethylene ether comonomer is one or more combination of oxk 501, oxk 608, Guangzhou Bofeng TPEG2400 or Jiangsu Hai' an TPEG (F-108);
the fully esterified isomeric ester is a Craine fully esterified isomeric ester, and the molecular weight is 1000-3000;
the unsaturated carboxylic acid comonomer is one or a combination of more of methacrylic acid, acrylic acid and maleic anhydride;
the reactive initiator is a mixture of an azo compound and a reducing agent, and the azo compound is one or a combination of two of azodiisobutyronitrile or azodiisoheptanonitrile; the reducing agent is one or more of sodium sulfite, L-ascorbic acid, sodium bisulfite, ferrous sulfate and sodium formaldehyde sulfoxylate;
the oxidant is peroxide, and the peroxide is one or a combination of hydrogen peroxide, ammonium persulfate, potassium persulfate and sodium persulfate.
8. A preparation method of the polycarboxylic acid high-performance water reducing agent with high water reduction and low collapse loss according to any one of claims 1 to 7, characterized by comprising the following steps:
(1) adding a high molecular weight methallyl alcohol polyoxyethylene ether comonomer and a reactive initiator into a four-neck flask provided with a stirrer and a thermometer, adding water, stirring for 5-10 min, and then simultaneously dropwise adding a material I solution and a material II solution;
(2) after the material I solution and the material II solution are dripped, preserving the heat for 0.5 to 1.5 hours at the temperature of between 35 and 45 ℃;
(3 after the reaction is finished, adding alkali liquor to neutralize the pH value of the solution to 6-7 when the temperature of the solution is cooled to 30 ℃.
9. The preparation method of the high water reducing and low collapse loss polycarboxylic acid high performance water reducing agent according to claim 8, characterized in that the material I solution is a solution prepared by uniformly stirring unsaturated carboxylic acid comonomer, fully esterified isomeric ester and water;
the material II solution is prepared by evenly stirring peroxide and water.
10. The preparation method of the high water reducing and low collapse loss polycarboxylic acid high performance water reducing agent according to claim 9, wherein the dripping duration of the material I solution is 2.5-3.5 h, and the dripping duration of the material II solution is 3-4 h.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113264741A (en) * | 2021-07-05 | 2021-08-17 | 洛阳理工学院 | 900 ℃ high-temperature-resistant C80 cement-based micro-expansion grouting material and preparation method and application thereof |
| CN113754839A (en) * | 2021-09-15 | 2021-12-07 | 广东瑞安科技实业有限公司 | Slow-release lignin-based polycarboxylic acid high-performance water reducing agent and preparation method thereof |
| CN115449022A (en) * | 2021-06-09 | 2022-12-09 | 武汉塔牌华轩新材料科技有限公司 | A kind of preparation method of high water-reducing powder polycarboxylate water-reducer |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102532435A (en) * | 2011-12-21 | 2012-07-04 | 湖北恒利建材科技有限公司 | Polycarboxylene high-performance water reducing agent and preparation method thereof |
| CN102815882A (en) * | 2012-08-03 | 2012-12-12 | 山西科腾环保科技有限公司 | High-performance water reducer of polycarboxylic acid, and preparation method thereof |
| CN107652404A (en) * | 2017-09-28 | 2018-02-02 | 四川铁科新型建材有限公司 | A kind of normal temperature synthesizing polyester polyether type of poly carboxylic acid and preparation method thereof |
-
2019
- 2019-12-24 CN CN201911348452.8A patent/CN111019063A/en not_active Withdrawn
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102532435A (en) * | 2011-12-21 | 2012-07-04 | 湖北恒利建材科技有限公司 | Polycarboxylene high-performance water reducing agent and preparation method thereof |
| CN102815882A (en) * | 2012-08-03 | 2012-12-12 | 山西科腾环保科技有限公司 | High-performance water reducer of polycarboxylic acid, and preparation method thereof |
| CN107652404A (en) * | 2017-09-28 | 2018-02-02 | 四川铁科新型建材有限公司 | A kind of normal temperature synthesizing polyester polyether type of poly carboxylic acid and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| 刘红霞等: "醚酯共聚类聚羧酸减水剂的合成与性能研究", 《江西建材》 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115449022A (en) * | 2021-06-09 | 2022-12-09 | 武汉塔牌华轩新材料科技有限公司 | A kind of preparation method of high water-reducing powder polycarboxylate water-reducer |
| CN113264741A (en) * | 2021-07-05 | 2021-08-17 | 洛阳理工学院 | 900 ℃ high-temperature-resistant C80 cement-based micro-expansion grouting material and preparation method and application thereof |
| CN113754839A (en) * | 2021-09-15 | 2021-12-07 | 广东瑞安科技实业有限公司 | Slow-release lignin-based polycarboxylic acid high-performance water reducing agent and preparation method thereof |
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