CN112876127A - Sodium-glucan modified polycarboxylic acid high-performance water reducing agent and preparation process thereof - Google Patents
Sodium-glucan modified polycarboxylic acid high-performance water reducing agent and preparation process thereof Download PDFInfo
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- CN112876127A CN112876127A CN202110164275.9A CN202110164275A CN112876127A CN 112876127 A CN112876127 A CN 112876127A CN 202110164275 A CN202110164275 A CN 202110164275A CN 112876127 A CN112876127 A CN 112876127A
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- reducing agent
- water reducing
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B40/00—Processes, in general, for influencing or modifying the properties of mortars, concrete or artificial stone compositions, e.g. their setting or hardening ability
- C04B40/0028—Aspects relating to the mixing step of the mortar preparation
- C04B40/0039—Premixtures of ingredients
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2103/00—Function or property of ingredients for mortars, concrete or artificial stone
- C04B2103/30—Water reducers, plasticisers, air-entrainers, flow improvers
- C04B2103/302—Water reducers
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Ceramic Engineering (AREA)
- Materials Engineering (AREA)
- Structural Engineering (AREA)
- Organic Chemistry (AREA)
- Curing Cements, Concrete, And Artificial Stone (AREA)
Abstract
The application relates to the field of concrete, and particularly discloses a sodium gluconate modified polycarboxylic acid high-performance water reducing agent and a preparation process thereof, wherein the modified polycarboxylic acid high-performance water reducing agent comprises 450 parts of methallyl alcohol polyoxyethylene ether 350-one, 65-75 parts of acrylic acid, 1-2 parts of 2-acrylamide-2-methacrylic sulfonic acid, 2-5 parts of mercaptoethanol, 2-5 parts of vitamin C and 80-110 parts of sodium gluconate; the preparation method comprises the following steps: adding methallyl alcohol polyoxyethylene ether, 2-acrylamide-2-methylpropanesulfonic acid, a dispersing agent and a tackifier into a reaction kettle, adding water to dissolve the methallyl alcohol polyoxyethylene ether, 2-acrylamide-2-methylpropanesulfonic acid, and adding hydrogen peroxide after the methyl allyl alcohol polyoxyethylene ether, the 2-acrylamide-2-methylpropanesulfonic acid, the dispersing agent and the tackifier are completely dissolved to obtain a premix; and (3) adding acrylic acid dropwise into the premix, and adjusting the pH value to be neutral to prepare the modified polycarboxylic acid high-performance water reducing agent.
Description
Technical Field
The application relates to the field of concrete, in particular to a sodium gluconate modified polycarboxylic acid high-performance water reducing agent and a preparation process thereof.
Background
The water reducing agent becomes an indispensable component of concrete, and plays an increasingly important role in improving the performance of concrete. As a concrete additive, the polycarboxylate superplasticizer has high water reducing rate, high plasticity retention, strong adaptability to cement, high strength of formed concrete, reduced post dryness, better corrosion resistance than the first and second generation superplasticizers in all aspects, energy conservation, environmental protection and green chemistry, is incomparable with other various water reducers, and has higher and higher requirements on slump retention performance of the polycarboxylate superplasticizer along with the development of commercial concrete.
In view of the above-mentioned related technologies, the inventors believe that in the concrete added with the polycarboxylic acid water reducing agent, since the main chain of the polycarboxylic acid is adsorbed on the surface of the cement particles to prevent the particles from contacting with water, and the side chain is a hydrophilic functional group providing electrostatic repulsion, the electrostatic repulsion causes mutual repulsion among the cement particles, and the finally prepared concrete has the defect of weak viscosity among the cement particles.
Disclosure of Invention
In order to improve the viscosity between cement particles in concrete, the application provides a sodium glucan modified polycarboxylic acid high-performance water reducing agent.
In order to obtain a sodium gluconate modified polycarboxylic acid high-performance water reducing agent, the application provides a preparation method of the sodium gluconate modified polycarboxylic acid high-performance water reducing agent.
In a first aspect, the application provides a modified polycarboxylic acid high-performance water reducing agent with sodium gluconate, which adopts the following technical scheme: the sodium gluconate modified polycarboxylic acid high-performance water reducing agent is prepared by stirring and mixing the following raw materials in parts by weight:
120 portions of methyl allyl alcohol polyoxyethylene ether 100-one,
65-75 parts of acrylic acid,
1-2 parts of 2-acrylamide-2-methacrylic sulfonic acid,
2-5 parts of mercaptoethanol,
90-100 parts of liquid caustic soda,
3-8 parts of hydrogen peroxide solution,
2-5 parts of vitamin C,
80-110 parts of sodium gluconate.
By adopting the technical scheme, after the polycarboxylate superplasticizer is added, the hydrophobic groups of the polycarboxylate superplasticizer can be directionally adsorbed on the surface of cement particles, the hydrophilic groups point to the aqueous solution, so that the surfaces of the cement particles have charges with the same sign, the cement particles are mutually repelled by electrostatic repulsion, the branched chain of the sodium gluconate is grafted on the main chain of the polycarboxylic acid, because the molecular structure of the sodium gluconate has longer alkyl groups which are adsorbed on the surfaces of a plurality of cement particles, the viscosity degree among the cement particles is increased, and the sodium gluconate molecule also contains hydroxyl which can form hydrogen bond with water to delay hydration of cement particles, therefore, the sodium gluconate modifies the polycarboxylate water reducer, and the prepared high-performance water reducer not only has the effect of delaying cement hydration, but also has the effect of improving concrete viscosity.
Preferably, the raw material of the water reducing agent comprises 30-50 parts of dispersing agent.
By adopting the technical scheme, the dispersing agent is added into the polycarboxylate water reducing agent, so that the mixing effect of the polycarboxylate water reducing agent in cement particles is better, the possibility of agglomeration of the polycarboxylate water reducing agent is reduced, the alkyl group of the sodium gluconate is adsorbed on the surfaces of the cement particles, and the effect of improving the viscosity between the cement particles is better.
Preferably, the dispersant is tricarboxybenzenesulfonic acid.
By adopting the technical scheme, the tricarboxybenzenesulfonic acid is used as the dispersing agent and is added into the water reducing agent, and the molecular formula of the tricarboxybenzenesulfonic acid contains carboxyl and sulfonic acid groups which have strong dispersibility, so that the water reducing agent can be fully dispersed in concrete by adding the tricarboxybenzenesulfonic acid, and the effect of improving the viscosity among cement particles is better.
Preferably, the water reducing agent raw material comprises 40-70 parts of tackifier.
Through adopting above-mentioned technical scheme, add the tackifier in the water-reducing agent raw materials, the tackifier can strengthen the cohesiveness between the cement granule, improves the viscidity between the cement granule to make the concrete that makes have the effect of high strength.
Preferably, the tackifier is methoxypolyethylene glycol maleamide.
By adopting the technical scheme, the methoxy polyethylene glycol maleic amide is used as a dispersing agent and is used for improving the viscosity of cement particles, the methoxy polyethylene glycol maleic amide contains an amide group, the amide group is connected with a main chain, the methoxy polyethylene glycol maleic amide is more stable in the alkaline environment of concrete and is more beneficial to the viscosity-increasing and water-retaining properties of the concrete, the amide group has a certain steric hindrance effect and can increase the dispersibility of the water reducing agent, and therefore, the effect of improving the viscosity of the concrete by adding the methoxy polyethylene glycol maleic amide is better.
Preferably, the mass concentration of the liquid caustic soda is 20-40%.
By adopting the technical scheme, when the mass concentration of the liquid caustic soda is controlled to be 20-40%, the cost performance of the prepared polycarboxylic acid high-performance water reducing agent is higher.
In a second aspect, the application provides a preparation method of a sodium gluconate modified polycarboxylic acid high-performance water reducing agent, which adopts the following technical scheme:
a preparation method of a sodium gluconate modified polycarboxylic acid high-performance water reducing agent comprises the following steps:
s1: adding methallyl alcohol polyoxyethylene ether, 2-acrylamide-2-methylpropanesulfonic acid, sodium gluconate, a dispersing agent and a tackifier into a reaction kettle, adding water to dissolve the methyl allyl alcohol polyoxyethylene ether, 2-acrylamide-2-methylpropanesulfonic acid, the sodium gluconate, the dispersing agent and the tackifier, adding the water to dissolve the methyl allyl alcohol polyoxyethylene ether, and adding the mixture into hydrogen peroxide after the methyl allyl alcohol polyoxyethylene ether, the 2-acrylamide-2-methylprop;
s2: heating the premix to 30-50 ℃, dropwise adding vitamin C, acrylic acid and mercaptoethanol into the premix, continuously preserving the temperature after dropwise adding is finished, and cooling to room temperature;
s3: and adjusting the pH value of the product to be neutral by adopting liquid caustic soda to prepare the modified polycarboxylic acid high-performance water reducing agent.
By adopting the technical scheme, the main chain of the prepared polycarboxylic acid water reducing agent is adsorbed on the surface of cement particles, the hydrophobic functional group alkyl of sodium gluconate is adsorbed on the surface of the cement particles, the viscosity of the cement particles is improved, and the tackifying water-retaining property of the polycarboxylic acid water reducing agent is improved as the sulfonic group and the amide group are respectively introduced into the dispersing agent and the tackifier, so that the polycarboxylic acid high-efficiency water reducing agent can be obtained by the preparation method.
In summary, the present application has the following beneficial effects:
1. because the sodium gluconate is adopted, the branched chain of the sodium gluconate is grafted on the main chain of the polycarboxylic acid, and the molecular structure of the sodium gluconate has longer alkyl groups, the alkyl groups are adsorbed on the surfaces of a plurality of cement particles, so that the viscosity degree among the cement particles is increased, and the sodium gluconate molecules also contain hydroxyl groups which can form hydrogen bonds with water, so that the hydration of the cement particles is delayed, and the effect of enhancing the viscosity of concrete is obtained;
2. methoxy polyethylene glycol maleic acid is preferably adopted in the application, methoxy polyethylene glycol maleic acid amide is used as a dispersing agent and is used for improving the viscosity of cement particles, the methoxy polyethylene glycol maleic acid amide contains an amide group, and the amide group is connected with a main chain, so that the cement particles are more stable in the alkaline environment of concrete, and the effect of thickening and water retention of the concrete is obtained;
3. the method comprises the steps of adding methallyl alcohol polyoxyethylene ether, 2-acrylamide-2-methylpropanesulfonic acid, sodium gluconate, a dispersing agent and a tackifier into a reaction kettle, adding water to dissolve the methyl allyl alcohol polyoxyethylene ether, the 2-acrylamide-2-methylpropanesulfonic acid, the dispersing agent and the tackifier, adding the water to dissolve the methyl allyl alcohol polyoxyethylene ether, and adding hydrogen peroxide into the reaction kettle after the methyl allyl alcohol polyoxyethylene ether, the 2-acrylamide-2-methylpropanesulfonic; raising the temperature, dropwise adding acrylic acid and mercaptoethanol into the premix, continuing to preserve heat after the dropwise adding is finished, and cooling to room temperature; the pH value of the product is adjusted to be neutral by adopting liquid caustic soda to prepare the modified polycarboxylic acid high-performance water reducing agent, so that the effect of increasing the viscosity of concrete is obtained.
Detailed Description
Source of raw materials
| Raw materials | Manufacturer of the product |
| Methallyl alcohol polyoxyethylene ether | Saint George chemical Co Ltd of Hebei |
| Acrylic acid | Shandong Ju & Biotechnology Co Ltd |
| 2-acrylamido-2-methylpropanesulfonic acid | SHOUGUANG ROSEN NEW MATERIAL Co.,Ltd. |
| Mercaptoethanol | Atte (Shandong) New Material Co Ltd |
| Liquid caustic soda | Jinan Xin Longglong Hai Industrial and trade Co Ltd |
| Hydrogen peroxide solution | Hebei Jiuxing chemical products Co Ltd |
| Vitamin C | Henan Lixiang Biotechnology Ltd |
| Sodium gluconate | Wujiang, Oubang Fine chemical Co Ltd |
| Tricarboxylic benzenesulfonic acids | Zhengzhou Akmm chemical Co Ltd |
| Methoxy polyethylene glycol maleamide | SHANGHAI YUANYE BIOTECHNOLOGY Co.,Ltd. |
Example 1
A sodium gluconate modified polycarboxylic acid high-performance water reducing agent is prepared by stirring and mixing the following raw materials:
110kg of methyl allyl alcohol polyoxyethylene ether,
70kg of acrylic acid was added to the reaction mixture,
1.5kg of 2-acrylamide-2-methacrylic sulfonic acid,
3.5kg of mercaptoethanol is added,
100kg of liquid caustic soda, wherein the mass concentration of the liquid caustic soda is 30 percent.
5.5kg of hydrogen peroxide solution,
3.5kg of vitamin C, and the like,
95kg of sodium gluconate is added into the mixture,
40kg of dispersing agent, wherein the dispersing agent is tricarboxybenzenesulfonic acid.
55kg of tackifier, wherein the tackifier is methoxy polyethylene glycol maleamide.
A preparation method of a sodium gluconate modified polycarboxylic acid high-performance water reducing agent comprises the following steps:
s1: adding methallyl alcohol polyoxyethylene ether, 2-acrylamide-2-methylpropanesulfonic acid, sodium gluconate, tricarboxybenzenesulfonic acid and methoxypolyethylene glycol maleic amide into a reaction kettle, adding hydrogen peroxide, and uniformly stirring to obtain a pre-mixture;
s2: when the temperature of the pre-mixture is raised to 40 ℃, dropwise adding vitamin C, acrylic acid and mercaptoethanol into the pre-mixture for 4 hours, continuously preserving the heat for 1.5 hours after the dropwise adding is finished, and cooling to the room temperature;
s3: and (3) adjusting the pH value of the product to 7 by adopting 30% liquid alkali to prepare the modified polycarboxylic acid high-performance water reducing agent.
According to the preparation method, the modified polycarboxylic acid high-performance water reducing agent is produced by changing the dosage of the raw materials and adding the modified polycarboxylic acid high-performance water reducing agent into the preparation method of the embodiment 2-5, the other operation steps and parameters are the same as those of the embodiment 1, and the polycarboxylic acid high-performance water reducing agent of the embodiment 1-5 is obtained, wherein the specific dosage of the embodiment 1-5 is shown in the table below.
Table 1, examples 1-5 details the raw materials used.
The concrete is prepared by stirring and mixing the following raw materials in parts by weight: 85kg of cement, 40kg of fly ash, 30kg of sand and 100kg of water, and the five polycarboxylic acid high-performance water reducing agents obtained in the above examples 1 to 5 were mixed with concrete raw materials respectively to obtain five high-viscosity concretes.
The high-viscosity concrete obtained in examples 1 to 5 was tested.
1. And (3) viscosity test: the viscosity of the concrete is tested by adopting an inverted slump cone method according to the standard of the test method for the performance of common concrete stirrers (GB/T50080-2016), and the longer the concrete flows out of the inverted slump cone means that the viscosity of the concrete is higher.
2. And (3) testing the compressive strength: the compressive strength of 7d and 28d, and the test method and the instrument are strictly executed according to GB/T50081-2019 common concrete mechanical property test method.
The test results are shown in the following table.
Table 2, results of testing concrete viscosity and concrete strength of examples 1-5.
As can be seen from the above table, the test results of example 1 are better than those of examples 2 to 5, and it can be seen that the concrete prepared in example 1 has strong compressive strength and high viscosity, so that the polycarboxylic acid water reducer prepared in example 1 is added into the concrete raw material to obtain high-viscosity concrete with high cost performance.
Example 6
A sodium gluconate modified polycarboxylic acid high-performance water reducing agent is based on the embodiment 1, a dispersing agent is not added into the polycarboxylic acid water reducing agent, and the rest operation steps and parameters are the same as those of the embodiment 1.
Example 7
A sodium gluconate modified polycarboxylic acid high-performance water reducing agent is based on example 1, barium stearate is selected as a dispersing agent, and the rest operation steps and parameters are the same as those in example 1.
Example 8
A sodium gluconate modified polycarboxylic acid high-performance water reducing agent is based on example 1, potassium citrate is selected as a dispersing agent, and the rest operation steps and parameters are the same as those in example 1.
Example 9
Based on the embodiment 1, no tackifier is added into the polycarboxylic acid water reducing agent, and the rest operation steps and parameters are the same as the embodiment 1.
Example 10
A sodium gluconate modified polycarboxylic acid high-performance water reducing agent is based on example 1, wherein a terpene resin is selected as a tackifier, and the rest operation steps and parameters are the same as those in example 1.
Example 11
A sodium gluconate modified polycarboxylic acid high-performance water reducing agent is based on example 1, ammonium oxide is selected as a tackifier, and the rest operation steps and parameters are the same as those in example 1.
Example 12
Based on the embodiment 1, the concentration of liquid caustic soda is selected to be 20%, and the rest operation steps and parameters are the same as those in the embodiment 1.
Example 13
Based on the embodiment 1, the concentration of liquid caustic soda is selected to be 40%, and the rest operation steps and parameters are the same as those in the embodiment 1.
Comparative example 1
A sodium gluconate modified polycarboxylic acid high-performance water reducing agent is based on the sodium gluconate modified polycarboxylic acid high-performance water reducing agent in the embodiment 1, and the rest operation steps and parameters are the same as those in the embodiment 1.
The concrete having high viscosity obtained in examples 6 to 13 and comparative example 1 was subjected to the test, and the test results are shown in the following table.
Table 3, test results of concrete viscosity and concrete strength of examples 6 to 13 and comparative example 1.
As can be seen from the above table, the test results of example 1 are significantly better than those of examples 6-13 and comparative example 1.
When the dispersant is not added to the polycarboxylate superplasticizer, the concrete prepared by adding the prepared polycarboxylate superplasticizer to the concrete raw material has a lower slump cone time and the compressive strength influence is not great, so that the slump cone time of the concrete can be improved by adding the dispersant, as can be seen by combining the example 1 and the example 6 with table 3.
It can be seen from the combination of examples 1 and 7 and table 3 that when barium stearate is used as the dispersant, the slump cone time of the obtained concrete is shorter, and when potassium citrate is used as the dispersant, the slump cone time of the obtained concrete is shorter and the compressive strength is lower, so that the fact that the slump cone time of the concrete can be prolonged and the compressive strength of the concrete can be enhanced by using tricarboxyphenylsulfonic acid as the dispersant can be obtained.
When the polycarboxylate water reducer is not added with the tackifier, the concrete prepared by adding the polycarboxylate water reducer into the concrete raw material has lower slump cone time and lower compressive strength, so that the concrete slump cone time can be prolonged and the compressive strength of the concrete can be enhanced by adding the tackifier.
When the terpene resin is used as the tackifier, the slump cone time of the obtained concrete is not much different from that of the concrete in example 1 but the compressive strength is lower as can be seen by combining the examples 1 and 10 and the table 3, and when the ammonium oxide is used as the tackifier, the slump cone time and the compressive strength of the obtained concrete are not much different from those of the concrete in example 1 but the slump cone time and the compressive strength of the obtained concrete are obviously better than those of the concrete in example 1 and the example 11, so that the slump cone time of the concrete obtained by using the methoxypolyethylene glycol maleamide as the tackifier is longer and the compressive strength is higher.
It can be seen from the combination of example 1 and example 12 and table 3 that when the concentration of liquid caustic soda is 20%, the slump cone time of the obtained concrete is low, and when the concentration of liquid caustic soda is 40%, the compressive strength of the obtained concrete is low, so that when the concentration of liquid caustic soda is 30%, the compressive strength of the obtained concrete is good, and the slump cone time is long.
When the sodium gluconate is not added into the polycarboxylate water reducer, the slump cone time of the obtained concrete is lower, and the compressive strength is obviously inferior to that of the concrete in example 1 by combining example 1 and comparative example 1 and table 3, so that the slump cone time of the concrete can be prolonged and the compressive strength of the concrete can be enhanced by adding the sodium gluconate.
The present embodiment is only for explaining the present application, and it is not limited to the present application, and those skilled in the art can make modifications of the present embodiment without inventive contribution as needed after reading the present specification, but all of them are protected by patent law within the scope of the claims of the present application.
Claims (7)
1. The sodium gluconate modified polycarboxylic acid high-performance water reducing agent is characterized by comprising the following components in percentage by weight: the material is prepared by stirring and mixing the following raw materials in parts by weight:
120 portions of methyl allyl alcohol polyoxyethylene ether 100-one,
65-75 parts of acrylic acid,
1-2 parts of 2-acrylamide-2-methacrylic sulfonic acid,
2-5 parts of mercaptoethanol,
90-100 parts of liquid caustic soda,
3-8 parts of hydrogen peroxide solution,
2-5 parts of vitamin C,
80-110 parts of sodium gluconate.
2. The sodium gluconate-modified polycarboxylic acid high-performance water reducing agent according to claim 1, which is characterized in that: the raw material of the water reducing agent comprises 30-50 parts of dispersing agent.
3. The sodium gluconate-modified polycarboxylic acid high-performance water reducing agent according to claim 2, which is characterized in that: the dispersant is tricarboxybenzenesulfonic acid.
4. The sodium gluconate-modified polycarboxylic acid high-performance water reducing agent according to claim 1, which is characterized in that: the raw material of the water reducing agent comprises 40-70 parts of tackifier.
5. The sodium gluconate-modified polycarboxylic acid high-performance water reducing agent according to claim 4, which is characterized in that: the tackifier is methoxy polyethylene glycol maleamide.
6. The sodium gluconate-modified polycarboxylic acid high-performance water reducing agent according to claim 1, which is characterized in that: the mass concentration of the liquid caustic soda is 20-40%.
7. The preparation method of the sodium gluconate-modified polycarboxylic acid high-performance water reducing agent according to any one of claims 1 to 6, which is characterized in that: the water reducing agent is prepared by the following steps:
s1: adding methallyl alcohol polyoxyethylene ether, 2-acrylamide-2-methylpropanesulfonic acid, sodium gluconate, a dispersing agent and a tackifier into a reaction kettle, adding water to dissolve the methyl allyl alcohol polyoxyethylene ether, 2-acrylamide-2-methylpropanesulfonic acid, the sodium gluconate, the dispersing agent and the tackifier, adding the water to dissolve the methyl allyl alcohol polyoxyethylene ether, and adding the mixture into hydrogen peroxide after the methyl allyl alcohol polyoxyethylene ether, the 2-acrylamide-2-methylprop;
s2: heating the premix to 30-50 ℃, dropwise adding vitamin C, acrylic acid and mercaptoethanol into the premix, continuously preserving the temperature after dropwise adding is finished, and cooling to room temperature;
s3: and adjusting the pH value of the product to be neutral by adopting liquid caustic soda to prepare the modified polycarboxylic acid high-performance water reducing agent.
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Application publication date: 20210601 |