CN114315203B - High-performance water reducing agent and preparation method thereof - Google Patents
High-performance water reducing agent and preparation method thereof Download PDFInfo
- Publication number
- CN114315203B CN114315203B CN202111647227.1A CN202111647227A CN114315203B CN 114315203 B CN114315203 B CN 114315203B CN 202111647227 A CN202111647227 A CN 202111647227A CN 114315203 B CN114315203 B CN 114315203B
- Authority
- CN
- China
- Prior art keywords
- water reducing
- solution
- reducing agent
- performance water
- product
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
- Y02W30/50—Reuse, recycling or recovery technologies
- Y02W30/91—Use of waste materials as fillers for mortars or concrete
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a high-performance water reducing agent and a preparation method thereof, wherein the preparation raw materials of the high-performance water reducing agent comprise 4-vinyl benzyl alcohol, lactobionic acid, p-carboxystyrene acrylic acid, sodium styrene sulfonate and unsaturated polyoxyethylene ether. According to the high-performance water reducing agent provided by the invention, phenyl groups are introduced into the branched chains containing sodium sulfonate and carboxyl, so that the stability and the strength are improved while the water reducing rate is ensured.
Description
Technical Field
The invention belongs to the technical field of concrete admixtures, and particularly relates to a high-performance water reducing agent and a preparation method thereof.
Background
The definition of the concrete admixture GB8076-2008 on the high-performance water reducing agent is as follows: the water reducing agent has higher water reducing rate, better slump constant retaining performance, less drying shrinkage and certain air entraining performance compared with the high-efficiency water reducing agent. The high-performance water reducing agent comprises a polycarboxylic acid water reducing agent, an aminocarboxylic acid water reducing agent and other water reducing agents which can meet the index requirement of the high-performance water reducing agent in the GB8076-2008 standard of concrete admixture.
At present, the Chinese high-performance water reducing agent is mainly represented by a polycarboxylic acid high-performance water reducing agent. It has the structural characteristic of comb shape, has the main chain with free carboxylic acid anion group and the composition of polyoxyethylene side chain, and can produce high-performance water reducing agent with different performances and characteristics by changing the type, proportion and reaction condition of the monomers.
With the development of times, people have higher and higher requirements on concrete, and the research on the water reducing agent also tends to be high-performance and multifunctional. People also find that the polycarboxylic acid high-performance water reducing agent has the advantages of high water reducing rate, good slump retaining property, low mixing amount and the like in the research process, but the stability of the polycarboxylic acid high-performance water reducing agent needs to be improved, and particularly the polycarboxylic acid high-performance water reducing agent has stronger selectivity when being compounded with other additives (such as an air entraining agent and a defoaming agent), so that different effects can be generated when the polycarboxylic acid high-performance water reducing agent is applied in different scenes, and the production is inconvenient.
In summary, how to design a high-performance water reducing agent and a preparation method thereof can improve the stability of the high-performance water reducing agent and the adaptability of the high-performance water reducing agent to other additives while ensuring the basic performance of the high-performance water reducing agent, and is a problem which needs to be solved urgently at present.
Disclosure of Invention
The invention aims to solve the technical problems and provides a high-performance water reducing agent, wherein phenyl is introduced into branched chains containing sodium sulfonate and carboxyl, so that the stability and the strength are improved while the water reducing rate is ensured.
The invention realizes the purpose by the following technical scheme, the preparation raw materials of the high-performance water reducing agent comprise 4-vinyl benzyl alcohol, lactobionic acid, p-carboxystyrene acrylic acid, sodium styrene sulfonate and unsaturated polyoxyethylene ether, and the molar ratio of the raw materials is 1: (0.8-1): (1.1-1.3): (1.2-1.5): (0.7-0.9).
Further, the molecular weight of the unsaturated polyoxyethylene ether is 500-2400, and specifically is allyl polyoxyethylene ether or isopentenyl polyoxyethylene ether.
The invention also provides a preparation method of the high-performance water reducing agent, which comprises the following steps:
(1) heating lactobionic acid to 120 ℃, adding a catalyst, uniformly mixing, then dropwise adding 4-vinyl benzyl alcohol, and carrying out esterification reaction under the stirring condition of 115 ℃ and 125 ℃ for 6-8h to obtain an esterification product;
(2) preparing p-carboxystyrene acrylic acid, 1/3 mass of initiator and pure water into a first solution, preparing sodium styrene sulfonate, 1/3 mass of initiator and pure water into a second solution, and preparing unsaturated polyoxyethylene ether monomer and pure water into a third solution for later use;
(3) dropwise adding the solution I into the solution III, stirring and reacting at 60-70 ℃ for 1-2h, then heating to 70-80 ℃, simultaneously dropwise adding the mixed solution of the residual 1/3 mass of the initiator and the esterification product and the solution II, controlling the dropwise adding speed of the solution II to be consistent, continuously reacting for 3-5h, naturally cooling the product to room temperature, and adding a sodium hydroxide solution to adjust the pH value to 7, thus obtaining the finished product of the high-performance water reducing agent.
Further, in the step (1), the catalyst is concentrated sulfuric acid, and the adding amount of the concentrated sulfuric acid is 1.5-2.5% of the total amount of the reactants.
In the step (2), the initiator is persulfate, and the mass ratio of the initiator to the unsaturated polyoxyethylene ether is (0.1-0.2): 100.
the invention also provides an air entraining agent used by matching with the high-performance water reducing agent, and the preparation raw materials of the air entraining agent comprise 3-chloro-2-hydroxy sodium propane sulfonate, p-carboxyphenylacetic acid and polyoxyethylene lauryl ether, and the molar ratio of the three components is 1: (1.1-1.3): (1.2-1.4).
Further, the preparation method of the air entraining agent specifically comprises the following steps:
s1, esterification: dropwise adding the mixed solution of the p-carboxyphenylacetic acid and the concentrated sulfuric acid into 3-chloro-2-sodium hydroxypropanesulfonate, and carrying out esterification reaction for 5-7h at the temperature of 100 ℃ and 110 ℃ under the stirring condition after the dropwise addition is finished to obtain a product I;
s2, hydrolysis reaction: uniformly mixing the product I and a sodium hydroxide solution in a reaction kettle, stirring and reacting for 4-5h at the temperature of 60-80 ℃, and then adjusting the pH of the solution to be neutral by using dilute sulfuric acid to obtain a product II;
s3, oxidation reaction: mixing the product II with an acidic potassium permanganate aqueous solution, stirring and reacting at 60-80 ℃ until the reaction solution fades, stopping the reaction, and extracting the reaction solution with carbon tetrachloride to obtain a product III;
s4, esterification: heating the polyoxyethylene lauryl ether to 110-120 ℃, then dropwise adding a mixed solution of the product III and concentrated sulfuric acid, continuing to perform heat preservation reaction for 6-8h after the dropwise adding is finished, and removing impurities from the obtained product to obtain the finished product of the air entraining agent.
Furthermore, the adding amount of concentrated sulfuric acid in the steps S1 and S4 is 2-3 percent of the total amount of reactants of each step, the mass concentration of the sodium hydroxide solution in the step S2 is 20-40 percent, and the adding amount is 10-20 times of the mass of the product.
Further, in the step S3, the mass concentration of the acidic potassium permanganate aqueous solution is 4-5%, and the adding amount is 30-40 times of the mass of the product II.
The impurity removal step in the step S4 is specifically: firstly, saturated sodium carbonate solution is used for extraction, and then saturated sodium chloride solution and saturated calcium chloride solution are used for washing in sequence.
The invention also provides a method for using the air entraining agent and the high-performance water reducing agent in a matching way, which comprises the following steps: mixing a high-performance water reducing agent and an air entraining agent, then performing spray drying to obtain powder, then adding a sodium alginate adhesive, uniformly mixing, introducing into a granulator to prepare particles of 160-200 meshes, then placing the particles in a calcium chloride solution, and standing for 1-3h to form gel microspheres; adding the gel microspheres into the cementing material, and mixing with water.
Furthermore, the mixing amount of the high-performance water reducing agent and the air entraining agent is 0.08-0.15% and 0.01-0.02% of the cementing material respectively.
The sodium alginate adhesive is prepared from sodium alginate and pure water according to the ratio of (3-5): 1, the addition amount of the sodium alginate adhesive is 3-5%, and the mass concentration of the calcium chloride solution is 6-8%.
The invention has the beneficial effects that:
(1) according to the high-performance water reducing agent prepared by the invention, phenyl groups are introduced into the branched chains containing sodium sulfonate and carboxyl, so that the stability and the strength are improved while the water reducing rate is ensured;
(2) the high-performance water reducing agent prepared by the invention has shorter branched chain containing phenyl group and is easy to bleed, so that the side chains of polyoxyethylene ether and lactobionic acid are grafted in the molecular main chain of the high-performance water reducing agent, the polyoxyethylene ether has good hydrophilicity and longer chain segment, and the lactobionic acid has good water-retaining property, thereby comprehensively reducing the bleeding phenomenon of the water reducing agent;
(3) the lactobionic acid is grafted in the high-performance water reducing agent, and the cohesiveness of cement can be further improved and the occurrence of segregation phenomenon can be reduced through the thickening effect of the lactobionic acid;
(4) because the adaptability of the existing polycarboxylic acid water reducing agent and the air entraining agent is poor and the performance stability of concrete is influenced, the air entraining agent used in combination with the high-performance water reducing agent is also prepared, one end of a molecular chain of the air entraining agent comprises hydrophilic sulfonic acid group, carboxyl group and polyoxyethylene chain segment, and the other end of the molecular chain of the air entraining agent is a nonpolar aliphatic hydrocarbon chain segment, so that the air entraining agent has excellent air entraining performance, and has good matching effect with the water reducing agent due to the similarity of the molecular structure and the group composition of the air entraining agent and the high-performance water reducing agent;
(5) the hydrophilic end of the air entraining agent takes the polyoxyethylene chain segment as a main chain, and the main chain is grafted with not only a branched chain containing carboxyl and double bonds, but also a branched chain containing sulfonic groups, so that the surface activity of the hydrophilic end of the air entraining agent is stronger, the performance of bubbles is good, and the amount of bubbles introduced into cement mortar is large;
(6) because the high-performance water reducing agent and the air entraining agent are rich in similar anions, an overlarge retarding effect is easily caused, and the hydration process of cement is influenced, the slow release treatment is carried out when the high-performance water reducing agent and the air entraining agent are used in a matched manner, so that the retarding effect is reduced;
(7) when the high-performance water reducing agent and the air entraining agent are used in a matched manner, the high-performance water reducing agent and the air entraining agent are granulated by adopting a sodium alginate adhesive, and then added into a calcium chloride solution to form gel microspheres, so that the high-performance water reducing agent and the air entraining agent are released in alkaline cement mortar due to the pH sensitivity of sodium alginate hydrogel, and a slow release effect is achieved.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
The embodiment provides a high-performance water reducing agent, and the preparation raw materials of the high-performance water reducing agent comprise 4-vinyl benzyl alcohol, lactobionic acid, p-carboxystyrene acrylic acid, sodium styrene sulfonate and allyl polyoxyethylene ether (molecular weight is 500-: 0.8: 1.1: 1.2: 0.7.
the preparation method of the high-performance water reducing agent specifically comprises the following steps:
(1) heating lactobionic acid to 120 ℃, adding concentrated sulfuric acid, uniformly mixing, adding the concentrated sulfuric acid with the addition amount of 1.5 percent of the total amount of reactants, then dropwise adding 4-vinyl benzyl alcohol, and carrying out esterification reaction at the temperature of 115 ℃ under the stirring condition for 6 hours to obtain an esterified product;
(2) preparing p-carboxystyrene acrylic acid, sodium persulfate of 1/3 mass and pure water into a solution I, preparing sodium styrene sulfonate, sodium persulfate of 1/3 mass and pure water into a solution II, and preparing allyl polyoxyethylene ether and pure water into a solution III for later use;
(3) dropwise adding the solution I into the solution III, stirring and reacting for 1h at 60 ℃, then heating to 70 ℃, simultaneously dropwise adding the remaining 1/3 mass of mixed solution of sodium persulfate and esterification products and the solution II, controlling the dropwise adding speed of the two to be consistent, continuing to react for 5h, naturally cooling the products to room temperature, adding a sodium hydroxide solution, and adjusting the pH value to 7 to obtain the finished product of the high-performance water reducing agent.
In the step (2), the mass ratio of the initiator sodium persulfate to the allyl polyoxyethylene ether is 0.1: 100.
example 2
On the basis of embodiment 1, this embodiment further provides an air-entraining agent used in combination with the high-performance water reducing agent, and the preparation raw materials of the air-entraining agent include sodium 3-chloro-2-hydroxypropanesulfonate, p-carboxyphenylacetic acid, and polyoxyethylene lauryl ether, and the molar ratio of the three is 1: 1.1: 1.2.
the preparation method of the air entraining agent specifically comprises the following steps:
s1, esterification: dropwise adding a mixed solution of p-carboxyphenylacetic acid and concentrated sulfuric acid into 3-chloro-2-sodium hydroxypropanesulfonate, and carrying out esterification reaction for 5 hours at 100 ℃ under a stirring condition to obtain a product I;
s2, hydrolysis reaction: uniformly mixing the first product and 10 times of sodium hydroxide solution (with the mass concentration of 40%) in a reaction kettle, stirring and reacting for 4 hours at the temperature of 60 ℃, and then adjusting the pH of the solution to be neutral by using dilute sulfuric acid to obtain a second product;
s3, oxidation reaction: mixing the second product with 30 times of acidic potassium permanganate aqueous solution (with the mass concentration of 5%), stirring at 60 ℃ to react until the reaction solution fades, stopping the reaction, and extracting the reaction solution with carbon tetrachloride to obtain a third product;
s4, esterification: heating lauryl alcohol polyoxyethylene ether to 110 ℃, then dropwise adding a mixed solution of a product III and concentrated sulfuric acid, continuing to perform heat preservation reaction for 6 hours after the dropwise adding is finished, extracting the obtained product with a saturated sodium carbonate solution, and then sequentially washing with a saturated sodium chloride solution and a saturated calcium chloride solution to obtain a finished product of the air entraining agent.
Wherein, the adding amount of concentrated sulfuric acid in the steps S1 and S4 is 2 percent of the total amount of reactants in each step.
The rest is the same as in example 1.
Example 3
On the basis of embodiment 2, the embodiment further provides a method for using the air entraining agent and the high-performance water reducing agent in a matching way, and the method specifically comprises the following steps: mixing a high-performance water reducing agent and an air entraining agent, then performing spray drying to obtain powder, then adding 3% of sodium alginate adhesive, uniformly mixing, introducing into a granulator to prepare 160-mesh granules, then placing the granules into a calcium chloride solution (with the mass concentration of 6%), and standing for 3 hours to form gel microspheres; adding the gel microspheres into the gel material, and mixing with water.
Wherein, the mixing amount of the high-performance water reducing agent and the air entraining agent is 0.08 percent and 0.01 percent of the gelled material respectively.
The sodium alginate adhesive is prepared from sodium alginate and pure water according to the weight ratio of 5: 1, and preparing the composition.
The rest is the same as in example 2.
Example 4
The embodiment provides a high-performance water reducing agent, and the preparation raw materials of the high-performance water reducing agent comprise 4-vinyl benzyl alcohol, lactobionic acid, p-carboxystyrene acrylic acid, sodium styrene sulfonate and allyl polyoxyethylene ether, and the molar ratio of the raw materials is 1: 0.9: 1.2: 1.35: 0.8.
the preparation method of the high-performance water reducing agent specifically comprises the following steps:
(1) heating lactobionic acid to 120 ℃, adding concentrated sulfuric acid, uniformly mixing, adding the concentrated sulfuric acid with the addition amount of 2% of the total amount of reactants, then dropwise adding 4-vinyl benzyl alcohol, and carrying out esterification reaction at the temperature of 120 ℃ under the condition of stirring for 7 hours to obtain an esterification product;
(2) preparing p-carboxystyrene acrylic acid, 1/3 mass of potassium persulfate and pure water into a solution I, preparing sodium styrene sulfonate, 1/3 mass of potassium persulfate and pure water into a solution II, and preparing allyl polyoxyethylene ether and pure water into a solution III for later use;
(3) dropwise adding the solution I into the solution III, stirring and reacting at 65 ℃ for 1.5h, then heating to 75 ℃, simultaneously dropwise adding the remaining 1/3 mass of mixed solution of potassium persulfate and esterification products and the solution II, controlling the dropwise adding speed of the two to be consistent, continuing to react for 4h, naturally cooling the products to room temperature, adding a sodium hydroxide solution, and adjusting the pH value to 7 to obtain the finished product of the high-performance water reducing agent.
In the step (2), the mass ratio of the initiator potassium persulfate to the initiator allyl polyoxyethylene ether is 0.15: 100.
the embodiment also provides an air entraining agent used in combination with the high-performance water reducing agent, and the preparation raw materials of the air entraining agent comprise 3-chloro-2-hydroxy sodium propane sulfonate, p-carboxyphenylacetic acid and polyoxyethylene lauryl ether, and the molar ratio of the three components is 1: 1.2: 1.3.
the preparation method of the air entraining agent specifically comprises the following steps:
s1, esterification: dropwise adding a mixed solution of p-carboxyphenylacetic acid and concentrated sulfuric acid into 3-chloro-2-sodium hydroxypropanesulfonate, and carrying out esterification reaction for 6 hours at 105 ℃ under the stirring condition after the dropwise addition is finished to obtain a product I;
s2, hydrolysis reaction: uniformly mixing 15 times of sodium hydroxide solution (with the mass concentration of 30%) in the first product in a reaction kettle, stirring and reacting for 4.5 hours at 70 ℃, and then adjusting the pH of the solution to be neutral by using dilute sulfuric acid to obtain a second product;
s3, oxidation reaction: mixing the second product with 35 times of acidic potassium permanganate aqueous solution (the mass concentration is 4.5%), stirring at 70 ℃ for reaction until the reaction liquid fades, stopping the reaction, and extracting the reaction liquid with carbon tetrachloride to obtain a third product;
s4, esterification: heating lauryl alcohol polyoxyethylene ether to 115 ℃, then dropwise adding a mixed solution of a product III and concentrated sulfuric acid, continuing to perform heat preservation reaction for 7 hours after the dropwise adding is finished, extracting the obtained product with a saturated sodium carbonate solution, and then sequentially washing with a saturated sodium chloride solution and a saturated calcium chloride solution to obtain a finished product of the air entraining agent.
Wherein, the adding amount of concentrated sulfuric acid in the steps S1 and S4 is 2.5 percent of the total amount of reactants in each step.
The embodiment also provides a method for matching the air entraining agent and the high-performance water reducing agent, which specifically comprises the following steps: mixing a high-performance water reducing agent and an air entraining agent, then performing spray drying to obtain powder, then adding 4% of sodium alginate binder, uniformly mixing, introducing into a granulator to prepare 180-mesh granules, then placing the granules into a calcium chloride solution (with the mass concentration of 7%), and standing for 2 hours to form gel microspheres; adding the gel microspheres into the gel material, and mixing with water.
Wherein, the mixing amount of the high-performance water reducing agent and the air entraining agent is 0.12 percent and 0.015 percent of the gelled material respectively.
The sodium alginate adhesive is prepared from sodium alginate and pure water according to the ratio of 4: 1, preparing the medicament.
Example 5
The embodiment also provides a high-performance water reducing agent, and the preparation raw materials of the high-performance water reducing agent comprise 4-vinyl benzyl alcohol, lactobionic acid, p-carboxystyrene acrylic acid, sodium styrene sulfonate and isopentenyl polyoxyethylene ether, and the molar ratio of the raw materials is 1: 1: 1.3: 1.5: 0.9.
the preparation method of the high-performance water reducing agent specifically comprises the following steps:
(1) heating lactobionic acid to 120 ℃, adding concentrated sulfuric acid, uniformly mixing, adding the concentrated sulfuric acid in an amount of 2.5 percent of the total amount of reactants, dropwise adding 4-vinyl benzyl alcohol, and performing esterification reaction at 125 ℃ under a stirring condition for 8 hours to obtain an esterification product;
(2) preparing p-carboxystyrene acrylic acid, 1/3 mass of ammonium persulfate and pure water into a solution I, preparing sodium styrene sulfonate, 1/3 mass of ammonium persulfate and pure water into a solution II, and preparing isopentenyl polyoxyethylene ether and pure water into a solution III for later use;
(3) and (3) dropwise adding the solution I into the solution III, stirring at 70 ℃ for reaction for 2h, heating to 80 ℃, simultaneously dropwise adding the remaining 1/3 mass of mixed solution of ammonium sulfate and esterification products and the solution II, controlling the dropwise adding speed of the solution II to be consistent, continuing the reaction for 3h, naturally cooling the products to room temperature, adding a sodium hydroxide solution, and adjusting the pH value to 7 to obtain the finished product of the high-performance water reducing agent.
In the step (2), the mass ratio of the initiator ammonium persulfate to the isopentenyl polyoxyethylene ether is 0.2: 100.
the embodiment also provides an air entraining agent used in combination with the high-performance water reducing agent, and the preparation raw materials of the air entraining agent comprise 3-chloro-2-hydroxy sodium propane sulfonate, p-carboxyphenylacetic acid and polyoxyethylene lauryl ether, and the molar ratio of the three components is 1: 1.3: 1.4.
The preparation method of the air entraining agent specifically comprises the following steps:
s1, esterification: dropwise adding a mixed solution of p-carboxyphenylacetic acid and concentrated sulfuric acid into 3-chloro-2-sodium hydroxypropanesulfonate, and carrying out esterification reaction for 7 hours at 110 ℃ under the stirring condition after the dropwise adding is finished to obtain a product I;
s2, hydrolysis reaction: uniformly mixing the product I and 20 times of sodium hydroxide solution (with the mass concentration of 20%) in a reaction kettle, stirring and reacting for 5 hours at the temperature of 80 ℃, and then adjusting the pH of the solution to be neutral by using dilute sulfuric acid to obtain a product II;
s3, oxidation reaction: mixing the second product with 40 times of acidic potassium permanganate aqueous solution (the mass concentration is 4%), stirring and reacting at 80 ℃ until the reaction solution fades, stopping the reaction, and extracting the reaction solution by carbon tetrachloride to obtain a third product;
s4, esterification: heating lauryl alcohol polyoxyethylene ether to 120 ℃, then dropwise adding a mixed solution of a product III and concentrated sulfuric acid, continuing to perform heat preservation reaction for 8 hours after the dropwise adding is finished, extracting the obtained product with a saturated sodium carbonate solution, and then sequentially washing with a saturated sodium chloride solution and a saturated calcium chloride solution to obtain a finished product of the air entraining agent.
Wherein, the adding amount of concentrated sulfuric acid in the steps S1 and S4 is 3 percent of the total amount of reactants in each step.
The embodiment also provides a method for matching the air entraining agent and the high-performance water reducing agent, which specifically comprises the following steps: mixing a high-performance water reducing agent and an air entraining agent, then performing spray drying to obtain powder, then adding 5% of sodium alginate binder, uniformly mixing, introducing into a granulator to prepare 200-mesh granules, then placing the granules into a calcium chloride solution (with the mass concentration of 8%), and standing for 1h to form gel microspheres; adding the gel microspheres into the cementing material, and mixing with water.
Wherein, the mixing amount of the high-performance water reducing agent and the air entraining agent is 0.15 percent and 0.012 percent of the gelled material respectively.
The sodium alginate adhesive is prepared from sodium alginate and pure water according to the weight ratio of 3: 1, and preparing the composition.
Comparative example 1
The comparative example is different from example 3 in that the high-performance water reducing agent is a commercially available polycarboxylic acid type high-performance water reducing agent.
Comparative example 2
The comparative example is different from example 3 in that the high-performance water reducing agent is a commercially available sulfamic acid high-performance water reducing agent.
Comparative example 3
This comparative example differs from example 4 in that the air-entraining agent is a commercially available alkylbenzene sulfonate type air-entraining agent.
Comparative example 4
This comparative example differs from example 4 in that the air-entraining agent is a commercially available rosin resin-based air-entraining agent.
Comparative example 5
The difference between the comparative example and the example 5 is that the method for matching the air entraining agent and the high-performance water reducing agent comprises the following specific steps: mixing the high-performance water reducing agent and the air entraining agent, spray-drying the mixture into powder, adding the powder into the cementing material, and mixing the powder with water.
Comparative example 6
The difference between the comparative example and the example 5 is that the method for matching the air entraining agent and the high-performance water reducing agent comprises the following specific steps: mixing the high-performance water reducing agent and the air entraining agent, then carrying out spray drying to obtain powder, then adding 5% of sodium alginate adhesive, uniformly mixing, then introducing into a granulator to prepare 200-mesh granules, then adding the granules into a cementing material, and mixing with water.
Comparative example 7
The difference between the comparative example and the example 5 is that in the method for using the air entraining agent and the high-performance water reducing agent in a matching way, sodium alginate is replaced by chitosan.
Comparative example 8
The difference between the comparative example and the example 5 is that in the method of using the air entraining agent and the high-performance water reducing agent together, sodium alginate is changed into starch.
Comparative example 9
The comparative example is different from example 5 in that the blending amount of the high-performance water reducing agent is 0.06%.
Comparative example 10
The difference between the comparative example and the example 5 is that the mixing amount of the high-performance water reducing agent is 0.18 percent.
Firstly, performance detection of the high-performance water reducing agent prepared by the invention
According to the standard type high-performance water reducing agent standard of GB8076 plus 2008 concrete admixture, the high-performance water reducing agent prepared in the embodiments 3-5 of the invention and the water reducing agents of the comparative examples 1 and 2 are added into the standard concrete for performance detection, and the results are shown in Table 1.
TABLE 1
From the results in Table 1, it is understood that the high-performance water reducing agents prepared by the methods of examples 3 to 5 of the present invention are superior in various performances, and show excellent water reducing performance with a water reducing ratio of 40% or more, as compared with comparative example 1 (a commercially available polycarboxylic acid type high-performance water reducing agent) and comparative example 2 (a commercially available sulfamic acid type high-performance water reducing agent).
Secondly, detecting the performance of the air entraining agent prepared by the invention
According to the air entraining agent standard in GB8076-2008 concrete admixture, the air entraining agents prepared in the embodiments 3-5 of the invention and the air entraining agents of the comparative examples 3 and 4 are added into the standard concrete for performance detection, and the results are shown in Table 2.
TABLE 2
From the results in Table 2, it is understood that the air-entraining agents prepared by the methods of examples 3 to 5 of the present invention are superior in various properties to those of comparative example 3 (commercially available alkylbenzene sulfonate type air-entraining agent) and comparative example 2 (commercially available rosin resin type air-entraining agent), that the air content is 6% or more, that the change in the air content over 1 hour is about 0.1%, and that the air-entraining agents exhibit superior air-entraining properties.
Thirdly, the test of the matching use of the high-performance water reducing agent prepared by the invention and the air entraining agent
1. Basic Performance test
The high performance water reducing agent and air entraining agent prepared in examples 3 to 5 of the present invention and comparative examples 1 to 4, 9 to 10 were applied to concrete formulation according to the method of use of the present invention, and then the basic properties of the concrete were measured, respectively, and the results are shown in table 3.
TABLE 3
The results in Table 3 show that the high-performance water reducing agent and the air entraining agent in examples 3 to 5 of the invention are combined for use, so that the concrete has stable properties and good adaptability.
Compared with example 3, comparative examples 1 and 2 change the type of the water reducing agent, and as a result, the gas content of the concrete is remarkably reduced; compared with the embodiment 4, the comparative examples 3 and 4 change the type of the air entraining agent, so that the performance indexes of the concrete, such as the water reducing rate, the bleeding rate ratio, the compressive strength ratio, the slump loss amount, the shrinkage ratio and the like, are obviously influenced; after the water reducing agent and the air entraining agent are changed randomly, the performance of the other additive is influenced, and the adaptability is weakened.
Compared with example 5, comparative examples 9 and 10 changed the amount of the water reducing agent, and as a result, the properties of the concrete were slightly reduced, which indicates that the performance of the concrete could be ensured only by using the water reducing agent in the amount according to the present invention.
Coagulation time test
Concrete was prepared according to the methods of examples 1 to 5 and comparative examples 5 to 10 of the present invention, wherein examples 1 and 2 were used by directly adding to a reference concrete according to the standard of GB 8076-.
TABLE 4
As is clear from the results in Table 4, the setting time of the concrete was remarkably shortened by using the high performance water reducing agent of examples 3 to 5 in combination with the air entraining agent according to the method of the present invention, as compared with those of comparative examples 5 to 8.
Compared with example 1, the concrete setting time is obviously prolonged by adding the air entraining agent directly in example 2. In order to solve the problem of slow setting caused by the addition of the air entraining agent, examples 3 to 5 provide a method for using the water reducing agent and the air entraining agent in a matched manner, specifically to perform slow release treatment so as to improve the slow setting phenomenon.
The invention has the beneficial effects that: according to the high-performance water reducing agent provided by the invention, phenyl groups are introduced into the branched chains containing sodium sulfonate and carboxyl, so that the stability and the strength are improved while the water reducing rate is ensured, and meanwhile, the air entraining agent matched with the water reducing agent is prepared, so that the air entraining agent is excellent in air entraining performance, and has good matching effect with the water reducing agent due to the similarity of the molecular structure and the group composition of the air entraining agent and the high-performance water reducing agent.
Finally, it should be noted that the above-mentioned embodiments are only preferred embodiments of the present invention, and not intended to limit the present invention, and although the present invention has been described in detail with reference to the foregoing embodiments, it will be apparent to those skilled in the art that modifications and equivalents can be made in the technical solutions described in the foregoing embodiments, or some technical features thereof can be replaced. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. A high-performance water reducing agent is characterized in that: the high-performance water reducing agent is prepared from 4-vinyl benzyl alcohol, lactobionic acid, p-carboxystyrene acrylic acid, sodium styrene sulfonate and unsaturated polyoxyethylene ether, wherein the molar ratio of the raw materials is 1: (0.8-1): (1.1-1.3): (1.2-1.5): (0.7-0.9).
2. The high performance water reducer of claim 1, characterized in that: the molecular weight of the unsaturated polyoxyethylene ether is 500-2400, and specifically is allyl polyoxyethylene ether or isopentenyl polyoxyethylene ether.
3. The preparation method of the high-performance water reducing agent according to claim 1, characterized by comprising the following steps: the method specifically comprises the following steps:
(1) heating lactobionic acid to 120 ℃, adding a catalyst, uniformly mixing, then dropwise adding 4-vinyl benzyl alcohol, and carrying out esterification reaction under the stirring condition of 115 ℃ and 125 ℃ for 6-8h to obtain an esterification product;
(2) preparing p-carboxystyrene acid, 1/3 mass of initiator and pure water into a first solution, preparing sodium styrene sulfonate, 1/3 mass of initiator and pure water into a second solution, and preparing unsaturated polyoxyethylene ether monomer and pure water into a third solution for later use;
(3) dropwise adding the solution I into the solution III, stirring and reacting at 60-70 ℃ for 1-2h, then heating to 70-80 ℃, simultaneously dropwise adding the mixed solution of the residual 1/3 mass of the initiator and the esterification product and the solution II, controlling the dropwise adding speed of the solution II to be consistent, continuously reacting for 3-5h, naturally cooling the product to room temperature, and adding a sodium hydroxide solution to adjust the pH value to 7, thus obtaining the finished product of the high-performance water reducing agent.
4. The preparation method of the high-performance water reducing agent according to claim 3, characterized in that:
in the step (1), the catalyst is concentrated sulfuric acid, and the adding amount of the concentrated sulfuric acid is 1.5-2.5% of the total amount of reactants;
in the step (2), the initiator is persulfate, and the mass ratio of the initiator to the unsaturated polyoxyethylene ether is (0.1-0.2): 100.
5. an air entraining agent used in combination with the high performance water reducing agent of claim 1, characterized in that: the air entraining agent is prepared from 3-chloro-2-hydroxypropanesulfonic acid sodium salt, p-carboxyphenylacetic acid and polyoxyethylene lauryl ether in a molar ratio of 1: (1.1-1.3): (1.2-1.4).
6. The air entraining agent according to claim 5, characterized in that: the preparation method of the air entraining agent specifically comprises the following steps:
s1, esterification: dropwise adding the mixed solution of the p-carboxyphenylacetic acid and the concentrated sulfuric acid into 3-chloro-2-sodium hydroxypropanesulfonate, and carrying out esterification reaction for 5-7h at the temperature of 100 ℃ and 110 ℃ under the stirring condition after the dropwise addition is finished to obtain a product I;
s2, hydrolysis reaction: uniformly mixing the product I and a sodium hydroxide solution in a reaction kettle, stirring and reacting for 4-5h at the temperature of 60-80 ℃, and then adjusting the pH of the solution to be neutral by using dilute sulfuric acid to obtain a product II;
s3, oxidation reaction: mixing the product II with an acidic potassium permanganate aqueous solution, stirring and reacting at 60-80 ℃ until the reaction solution fades, stopping the reaction, and extracting the reaction solution with carbon tetrachloride to obtain a product III;
s4, esterification: heating the polyoxyethylene lauryl ether to 110-120 ℃, then dropwise adding a mixed solution of the product III and concentrated sulfuric acid, continuing to perform heat preservation reaction for 6-8h after the dropwise adding is finished, and removing impurities from the obtained product to obtain the finished product of the air entraining agent.
7. The air entraining agent according to claim 6, characterized in that: the adding amount of concentrated sulfuric acid in the steps S1 and S4 is 2-3% of the total amount of reactants in each step, the mass concentration of the sodium hydroxide solution in the step S2 is 20-40%, and the adding amount is 10-20 times of the mass of the product.
8. The air entraining agent according to claim 6, characterized in that:
in the step S3, the mass concentration of the acidic potassium permanganate aqueous solution is 4-5%, and the adding amount is 30-40 times of the mass of the product II;
the impurity removal step in the step S4 is specifically: firstly, extracting with saturated sodium carbonate solution, and then washing with saturated sodium chloride solution and saturated calcium chloride solution in sequence.
9. A method for using the air entraining agent according to any one of claims 5 to 8 in combination with the high performance water reducing agent according to any one of claims 1 to 4, characterized in that: mixing a high-performance water reducing agent and an air entraining agent, then performing spray drying to obtain powder, then adding a sodium alginate adhesive, uniformly mixing, introducing into a granulator to prepare particles of 160-200 meshes, then placing the particles in a calcium chloride solution, and standing for 1-3h to form gel microspheres; adding the gel microspheres into the gel material, and mixing with water.
10. The method for using the air entraining agent and the high-performance water reducing agent together according to claim 9 is characterized in that:
the mixing amount of the high-performance water reducing agent and the air entraining agent is 0.08-0.15% and 0.01-0.02% of the cementing material respectively;
the sodium alginate adhesive is prepared from sodium alginate and pure water according to the ratio of (3-5): 1, the addition amount of the sodium alginate adhesive is 3-5%, and the mass concentration of the calcium chloride solution is 6-8%.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111647227.1A CN114315203B (en) | 2021-12-31 | 2021-12-31 | High-performance water reducing agent and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111647227.1A CN114315203B (en) | 2021-12-31 | 2021-12-31 | High-performance water reducing agent and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN114315203A CN114315203A (en) | 2022-04-12 |
| CN114315203B true CN114315203B (en) | 2022-09-09 |
Family
ID=81017039
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202111647227.1A Active CN114315203B (en) | 2021-12-31 | 2021-12-31 | High-performance water reducing agent and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN114315203B (en) |
Family Cites Families (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102336845B (en) * | 2010-07-27 | 2014-04-30 | 上海台界化工有限公司 | Method for synthesizing polycarboxylic acid water reducer |
| CN102372467B (en) * | 2010-08-24 | 2013-09-11 | 上海台界化工有限公司 | Method for preparing low-strength concrete by using polycarboxylate superplasticizer |
| CN102286134A (en) * | 2011-06-09 | 2011-12-21 | 江苏天音化工有限公司 | Preparation method for high-performance water reducing agent |
| JP5801695B2 (en) * | 2011-11-10 | 2015-10-28 | 株式会社日本触媒 | Method for producing copolymer for cement admixture |
| CN102951865B (en) * | 2012-11-01 | 2014-06-04 | 重庆健杰科技有限公司 | Air entraining type poly carboxylic acid high performance water reducing agent and preparation method thereof |
| CN111377647A (en) * | 2018-12-30 | 2020-07-07 | 南宁砼材科技有限责任公司 | Preparation method of air entraining agent applied to preparation of modified cassava starch-polycarboxylic acid composite water reducing agent |
-
2021
- 2021-12-31 CN CN202111647227.1A patent/CN114315203B/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| CN114315203A (en) | 2022-04-12 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN108659177B (en) | High-adaptability ultra-long slow-release slump retaining agent and preparation method thereof at normal and low temperature | |
| CN114195421B (en) | Preparation method of polycarboxylic acid additive for machine-made sand concrete | |
| WO2016026346A1 (en) | Low-temperature method for preparing high-adaptability ether polycarboxylic acid water reducer | |
| CN105837763B (en) | Silane polycarboxylic acid water reducing agent and preparation method thereof | |
| CN107827388B (en) | High-performance compound polycarboxylate superplasticizer | |
| CN111925489B (en) | High-water-reduction slump-retaining type polycarboxylate superplasticizer and preparation method and application thereof | |
| CN103693883A (en) | Collapse prevention type polycarboxylic acid water reducing agent and preparation method thereof | |
| CN104692701A (en) | Room-temperature synthetic type polycarboxylic high performance water-reducing agent and preparation method thereof | |
| CN105330835A (en) | Alpha-acrylamido-omega-methoxy polyethylene glycol active macromonomer and preparation method thereof | |
| CN102503216A (en) | Method for synthesizing universal polycarboxylic water reducer | |
| CN114315203B (en) | High-performance water reducing agent and preparation method thereof | |
| CN106699965A (en) | Concrete performance regulator and preparation method thereof | |
| CN109627394A (en) | A kind of polycarboxylate concrete dehydragent and preparation method thereof being adapted to Machine-made Sand | |
| CN108586672A (en) | A kind of cross-linking type polycarboxylic acid super-plasticizer and its preparation method and application | |
| CN109721271B (en) | Polycarboxylate water reducing agent composition for self-compacting high-workability concrete | |
| CN108706899B (en) | Preparation method of modified cement dispersant | |
| CN103724560B (en) | A kind of superpower slump retaining agent and working method thereof | |
| CN110746549B (en) | Ultra-long slow-release polycarboxylic slump retaining agent and preparation method thereof | |
| CN111620594B (en) | Polycarboxylate superplasticizer and preparation method thereof | |
| CN108395138A (en) | A kind of accelerator for cement slurry | |
| CN110255958B (en) | Wet-mixed mortar plasticity stabilizer and preparation method thereof | |
| CN104530325B (en) | A kind of preparation method of high-performance polycarboxylic acids water reducing agent | |
| CN109111556B (en) | Ester ether crosslinking polycarboxylic acid workability regulator and preparation method thereof | |
| CN103922629A (en) | Polycarboxylic acid high-performance water reducer | |
| CN111825372A (en) | Polycarboxylic acid high-performance water reducing agent and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |