WO2020192140A1 - High-intensity solubilizing liquid accelerator and preparation method therefor - Google Patents

Abstract

A high-intensity solubilizing liquid accelerator and a preparation method therefor, the liquid accelerator at least comprising the following raw materials in parts by weight: 30 to 40 parts of aluminum sulfate, 5 to 10 parts of aluminum citrate, 2 to 8 parts of hydroxyethyl cellulose, 1 to 10 parts of pH regulators, 5 to 15 parts of complexing enhancers, 0.5 to 3 parts of stabilizing agents and the balance of water. With the introduction of hydroxyethyl cellulose for synthesizing the liquid accelerator and the combination of the complexing enhancers, stabilizing agents and the hydroxyethyl cellulose in the solution, a crosslinked reticular structure is formed, a good solubilizing effect may be achieved, the product concentration is as high as 80%, phenomena of layering and precipitation separation cannot occur, the product dissolution effect is good, and the transportation cost of the liquid accelerator may be reduced.

Description

High-strength solubilizing liquid quick-setting agent and preparation method thereof Technical field

The invention belongs to the technical field of building materials, and specifically relates to a high-strength solubilizing liquid accelerator and a preparation method thereof.

Background technique

Accelerating agent is a new type of chemical admixture that can quickly set and harden cement concrete. In order to increase the thickness of a shotcrete spray layer, the shotcrete must be mixed with an accelerator to shorten the time interval between two shots and improve The early strength of shotcrete reduces the rebound amount of shotcrete and guarantees the stability of the project quality. It is mainly used for bolting and shotcrete support in tunnels, shafts, slope protection and other projects, as well as in the process of plugging and repairing.

There are many types of accelerators. According to the nature and state of accelerators, they can be roughly divided into four types: alkaline powder accelerators, alkali-free powder accelerators, alkaline liquid accelerators and alkali-free liquid accelerators . Compared with powdered accelerators, liquid accelerators mix more uniformly with materials, improve the quality of shotcrete and overcome the shortcomings of powder accelerators with large dust and large resilience. There are alkali liquid accelerators. Because of the high alkali content, the strength and durability of concrete will decrease in the later stage. In addition, it may also cause environmental pollution, especially groundwater environment pollution. Compared with traditional powder quick-setting admixtures and alkali-free liquid quick-setting admixtures, it can effectively overcome the above shortcomings and has become a research hotspot. However, the current production and application of alkali-free liquid accelerators also have many problems. For example, the development of concrete strength is unstable, the product is prone to stratification and precipitation, the stability is not good, the production concentration cannot be increased, and the concentration is increased. Poor product stability and high transportation costs make the quality of shotcrete unstable during the construction process, which brings safety hazards to production and construction. Therefore, it is of great significance to develop a liquid accelerator that can increase concrete strength, increase concentration, good stability, and low alkali content.

Summary of the invention

The purpose of the present invention is to provide a high-strength solubilizing liquid quick-setting admixture and a preparation method thereof, so as to solve the problems of poor stability of the existing quick-setting admixtures, easy stratification and precipitation, and the production concentration cannot be increased.

In order to achieve the above-mentioned object, the technical scheme of the present invention is as follows: a high-strength solubilizing liquid accelerator, by weight, at least contains the following preparation raw materials:

Preferably, the preparation method of the complexing enhancer is to add ethylenediaminetetraacetic acid to the reaction kettle, turn on the stirring device, and then add alcoholamine and catalyst all at once to react, and at a temperature of 70-100°C, Reacting for 1 to 4 hours to prepare the complex enhancer, wherein the molar ratio of ethylenediaminetetraacetic acid and alcohol amine is 1:0.5-2, and the amount of catalyst is 0.5 to 0.5 of the total mass of ethylenediaminetetraacetic acid and alcohol amine. 3.0%.

Preferably, the alcohol amine is at least one of monoethanolamine, diethanolamine, triethanolamine, triisopropanolamine and diethanolmonoisopropanolamine.

Preferably, the catalyst is p-toluenesulfonic acid and/or concentrated sulfuric acid.

Preferably, the preparation method of the stabilizer is: adding bottom water to the reaction vessel, turning on the stirring device, controlling the temperature of the reaction vessel to 20-50°C, and then adding the unsaturated fluorine-containing compound aqueous solution, the acrylic acid aqueous solution, and the The initiator aqueous solution and the molecular weight regulator aqueous solution, the dripping time is 1.0-4.0h, after the dripping is completed, the temperature is 20-50℃ and the reaction is kept for 0-3.0h to prepare the stabilizer, wherein, this step The total amount of water used is such that the mass concentration of the stabilizer is 5-40%, the mass ratio of unsaturated fluorine-containing compound and acrylic acid is 1:1 to 3, and the amount of initiator is the total mass of unsaturated fluorine-containing compound and acrylic acid. 0.5 to 3.5% of the molecular weight, and the amount of the molecular weight regulator is 0.2 to 2.5% of the total mass of the unsaturated fluorine-containing compound and acrylic acid.

Preferably, the unsaturated fluorine-containing compound is 2-fluoro cinnamic acid, 3-fluoro cinnamic acid, 4-fluoro cinnamic acid, 2-(trifluoromethyl) cinnamic acid, 3-(trifluoromethyl) cinnamic acid and 4 -At least one of (trifluoromethyl) cinnamic acid.

Preferably, the initiator is ammonium persulfate.

Preferably, the molecular weight regulator is at least one of thioglycolic acid, mercaptopropionic acid and mercaptoethanol.

Preferably, the pH adjusting agent is at least one of concentrated sulfuric acid, p-toluenesulfonic acid, citric acid, tartaric acid, salicylic acid, oxalic acid, and hydrofluoric acid.

The method for preparing a high-strength solubilizing liquid quick-setting agent provided by the present invention specifically includes the following steps: firstly, the stabilizer and water are added to the reaction kettle for stirring, and then the pH adjuster is added and stirred uniformly, and then added separately Stir aluminum sulfate, aluminum citrate, hydroxyethyl cellulose and complexing enhancer. After the materials are completely stirred and evenly mixed, react for 1.0-4.0h at a temperature of 40-80°C. After the reaction is completed, the product High-strength solubilizing liquid accelerator.

The beneficial effects of the present invention are:

1. In the present invention, a complexing enhancer is prepared by esterifying ethylenediaminetetraacetic acid and an alcohol amine, which is used in the synthesis of a liquid accelerator, which can improve the overall strength of concrete.

2. In the present invention, a stabilizer is prepared by copolymerizing an unsaturated fluorine-containing compound and acrylic acid, and then applied to the synthesis of a liquid accelerator, which can improve the stability of the product.

3. In the present invention, hydroxyethyl cellulose is used to synthesize liquid quick-setting agent, and the complexation enhancer, stabilizer and hydroxyethyl cellulose are combined in the solution to form a cross-linked network structure, which can achieve good solubilization Effectively, the product concentration can be as high as 80%, and there will be no stratification or precipitation. The product has a good dissolution effect and can reduce the transportation cost of the liquid accelerator.

detailed description

In order to make the technical problems, technical solutions, and beneficial effects solved by the present invention clearer, the present invention will be further described in detail below in conjunction with embodiments. It should be understood that the specific embodiments described here are only used to explain the present invention, but not to limit the present invention.

Example 1

(1) Preparation of complexing enhancer: Add 100.00g of ethylenediaminetetraacetic acid to the reaction kettle, turn on the stirring device, and then add 24.00g of monoethanolamine and 1.20g of p-toluenesulfonic acid at one time to react at a temperature of 80 React for 3h at ℃ to obtain the complex enhancer;

(2) Preparation of stabilizer: Add 100.00g of bottom water to the reactor, turn on the stirring device, control the temperature of the reactor to 40℃, and then add drops of 2-fluorocinnamic acid and 3-fluorocinnamic acid to the reactor. Mixed solution (18.00g of 2-fluorocinnamic acid, 2.00g of 3-fluorocinnamic acid, 20.00g of water), aqueous acrylic acid solution (46.00g of acrylic acid, 20.00g of water), aqueous ammonium persulfate (of which Ammonium sulfate is 1.00g, water is 10.00g) and thioglycolic acid aqueous solution (where thioglycolic acid is 0.60g, water is 10.00g), the dripping time is 2.0h, after the dripping is completed, at a temperature of 40℃, Insulate for 1.0h to prepare stabilizer;

(3) Add 2.00g of the stabilizer prepared in step (2) and 60.00g of water into the reaction kettle for stirring, then add 5.00g of concentrated sulfuric acid, and then add 37.00g of aluminum sulfate and 8.00g of aluminum citrate, respectively , 6.00g of hydroxyethyl cellulose and 12.00g of the complexing enhancer prepared in step (1) are stirred. After the materials are completely stirred and evenly mixed, they will react for 3.0h at a temperature of 50°C to obtain a high-strength solubilization Type liquid quick-setting agent KZJ-1.

Example 2

(1) Preparation of complexing enhancer: Add 100.00g of ethylenediaminetetraacetic acid to the reaction kettle, turn on the stirring device, and then add 36.00g of diethanolamine and 2.00g of concentrated sulfuric acid at one time to react at a temperature of 90°C , React for 3h to obtain the complex enhancer;

(2) Preparation of stabilizer: add 100.00g of bottom water to the reaction kettle, turn on the stirring device, control the temperature of the reaction kettle to 30℃, and then add drops of 2-fluorocinnamic acid and 4-fluorocinnamic acid to the reaction kettle respectively. Mixed solution (wherein 2-fluorocinnamic acid is 10.00g, 4-fluorocinnamic acid is 10.00g, water is 20.00g), acrylic acid aqueous solution (including acrylic acid is 37.00g, water is 20.00g), ammonium persulfate aqueous solution (among them Ammonium sulfate is 1.70g, water is 10.00g) and mercaptopropionic acid aqueous solution (among which mercaptopropionic acid is 1.00g, water is 10.00g), the dripping time is 3.0h, after the dripping is completed, the temperature is 30℃. After heat preservation for 1.0h, the stabilizer is prepared;

(3) Add 1.80g of the stabilizer prepared in step (2) and 30.00g of water to the reaction kettle for stirring, then add 8.00g of oxalic acid, and then add 30.00g of aluminum sulfate and 6.00g of citric acid, respectively Aluminium, 5.00g hydroxyethyl cellulose and 8.00g of the complexing enhancer prepared in step (1) are stirred. After the materials are completely stirred and evenly mixed, they are reacted for 2.0h at a temperature of 60°C to obtain a high-strength enhancement. Dissolved liquid quick-setting agent KZJ-2.

Example 3

(1) Preparation of complexing enhancer: Add 100.00g of ethylenediaminetetraacetic acid to the reaction kettle, turn on the stirring device, and then add 39.00g of triethanolamine and 2.70g of concentrated sulfuric acid at one time to react at a temperature of 70°C , React for 4h to obtain the complex enhancer;

(2) Preparation of stabilizer: add 100.00g of bottom water to the reactor, turn on the stirring device, control the temperature of the reactor to 50℃, and then add 3-fluorocinnamic acid and 2-(trifluoromethyl) to the reactor. Base) cinnamic acid mixed solution (wherein 3-fluoro cinnamic acid is 16.00g, 2-(trifluoromethyl) cinnamic acid is 4.00g, water is 20.00g), acrylic acid aqueous solution (wherein acrylic acid is 50.00g, water is 20.00 g). Ammonium persulfate aqueous solution (Ammonium persulfate is 2.00g, water is 10.00g) and mercaptoethanol aqueous solution (Mercaptoethanol is 1.40g, water is 10.00g), the dropping time is 2.0h, after the dropping is completed , At a temperature of 50℃, keep for 0.5h to prepare stabilizer;

(3) Add 3.00g of the stabilizer prepared in step (2) and 20.00g of water to the reaction kettle for stirring, then add 6.00g of hydrofluoric acid, and after stirring, add 32.00g of aluminum sulfate and 7.00g of citric acid, respectively Aluminum, 8.00g of hydroxyethyl cellulose and 10.00g of the complexing enhancer prepared in step (1) are stirred. After the materials are completely stirred and evenly mixed, they are reacted for 1.5 hours at a temperature of 70°C to obtain a high-strength enhancement. Dissolved liquid quick-setting agent KZJ-3.

Example 4

(1) Preparation of complexing enhancer: Add 100.00g of ethylenediaminetetraacetic acid to the reaction kettle, turn on the stirring device, and add 69.00g of triisopropanolamine and 3.60g of concentrated sulfuric acid to react at the temperature React for 2h at 100°C to obtain the complex enhancer;

(2) Preparation of stabilizer: Add 100.00g of bottom water to the reactor, turn on the stirring device, control the temperature of the reactor to 20℃, and then add 4-fluorocinnamic acid and 3-(trifluoromethyl) to the reactor. Base) cinnamic acid mixed solution (where 4-fluoro cinnamic acid is 6.00g, 3-(trifluoromethyl) cinnamic acid is 14.00g, water is 20.00g), acrylic acid aqueous solution (wherein acrylic acid is 28.00g, water is 20.00 g), ammonium persulfate aqueous solution (Ammonium persulfate is 0.80g, water is 10.00g) and thioglycolic acid aqueous solution (among which thioglycolic acid is 0.70g, water is 10.00g), the dripping time is 3.0h, after the dripping is completed , At a temperature of 20℃, keep for 2.0h to prepare stabilizer;

(3) Add 2.60g of the stabilizer prepared in step (2) and 50.00g of water to the reactor and stir, then add 10.00g of concentrated sulfuric acid, and after stirring, add 36.00g of aluminum sulfate and 10.00g of aluminum citrate respectively , 3.00g of hydroxyethyl cellulose and 15.00g of the complexing enhancer prepared in step (1) are stirred. After the materials are completely stirred and uniform, the reaction is carried out for 2.0h at a temperature of 80℃ to obtain a high-strength solubilization Type liquid quick-setting agent KZJ-4.

Example 5

(1) Preparation of complexing enhancer: Add 100.00g of ethylenediaminetetraacetic acid to the reaction kettle, turn on the stirring device, and then add 46.00g of diethanolmonoisopropanolamine and 3.20g of p-toluenesulfonic acid in one time. Reaction, at a temperature of 85°C, react for 2 hours to obtain a complex enhancer;

(2) Preparation of stabilizer: add 100.00g of bottom water to the reactor, turn on the stirring device, control the temperature of the reactor to 35°C, and then add 2-fluorocinnamic acid and 4-(trifluoromethyl) to the reactor. Base) cinnamic acid mixed solution (wherein 2-fluoro cinnamic acid is 7.00g, 4-(trifluoromethyl) cinnamic acid is 13.00g, water is 20.00g), acrylic acid aqueous solution (wherein acrylic acid is 42.00g, water is 20.00 g). Ammonium persulfate aqueous solution (Ammonium persulfate is 2.60g, water is 10.00g) and mercaptopropionic acid aqueous solution (Mercaptopropionic acid is 1.20g, water is 10.00g), dripping time is 2.5h, drip After completion, the stabilizer is prepared by keeping the temperature at 35℃ for 2.0h;

(3) Add 2.50g of the stabilizer prepared in step (2) and 40.00g of water to the reaction kettle for stirring, then add 7.00g of oxalic acid, and then add 35.00g of aluminum sulfate and 9.00g of citric acid, respectively Aluminum, 7.00g of hydroxyethyl cellulose and 11.00g of the complexing enhancer prepared in step (1) are stirred evenly. After the materials are fully stirred, the reaction is carried out for 2.0h at a temperature of 40℃ to obtain a high-strength enhancement. Dissolved liquid quick-setting agent KZJ-5.

The high-strength solubilizing liquid accelerator prepared in Example 1 to Example 5 was tested, and Conch P.O 42.5 ordinary Portland cement was selected. According to GB/T35159-2017 "Accelerating Agent for Shotcrete", the obtained high-strength solubilizing liquid accelerator was tested for cement slurry setting water time and cement mortar strength. The amount of accelerator is calculated as the percentage of cement weight.

Cement paste setting time test

Cement 400g

Water 140g

Cement mortar strength test

Cement 900g

Standard sand 1350g

Water 450g

The accelerator is added to the cement paste according to 6%-9% of the weight of the cement, and the above water consumption includes the water contained in the liquid accelerator. With the current commercially available liquid accelerator (Sample 1) as a comparison, the cement slurry setting time, mortar strength, stability and solid content of the liquid accelerator were tested. The test results are shown in Tables 1 and 2.

Table 1 Test results of cement paste setting time

Table 2 Strength test and stability of cement mortar

It can be seen from Table 1 and Table 2 that the initial setting time and final setting time of the high-strength solubilizing liquid accelerator of the present invention are shorter than those of the commercially available liquid accelerator. The 1d compressive strength, 28d compressive strength ratio and The 90d compressive strength retention rate is higher, the solid content is higher and the stability is better.

The above descriptions are only preferred embodiments of the present invention and are not intended to limit the present invention. Therefore, as long as any modification, equivalent replacement and improvement made by using the content of the present invention specification, they should be included in the protection scope of the present invention. Inside.

Claims (10)

1. A high-strength solubilizing liquid quick-setting agent, characterized in that: the liquid quick-setting agent, by weight, contains at least the following preparation raw materials:

   
2. A high-strength solubilizing liquid quick-setting agent according to claim 1, characterized in that: the preparation method of the complexation enhancer is to add ethylenediaminetetraacetic acid into the reactor, turn on the stirring device, and then Add alcohol amine and catalyst at one time to react, and react for 1 to 4 hours at a temperature of 70-100°C to prepare the complex enhancer, wherein the molar ratio of ethylenediaminetetraacetic acid to alcoholamine is 1 : 0.5-2, the amount of the catalyst is 0.5-3.0% of the total mass of ethylenediaminetetraacetic acid and alcoholamine.
3. A high-strength solubilizing liquid quick-setting agent according to claim 2, wherein the alcohol amine is monoethanolamine, diethanolamine, triethanolamine, triisopropanolamine and diethanolmonoisopropanolamine. At least one of.
4. The high-strength solubilizing liquid accelerator according to claim 2, wherein the catalyst is p-toluenesulfonic acid and/or concentrated sulfuric acid.
5. The high-strength solubilizing liquid quick-setting agent according to claim 1, wherein the preparation method of the stabilizer is: adding bottom water to the reaction vessel, turning on the stirring device, and controlling the temperature of the reaction vessel to 20~ At 50℃, add the unsaturated fluorine-containing compound aqueous solution, acrylic acid aqueous solution, initiator aqueous solution and molecular weight regulator aqueous solution into the reaction kettle respectively. The dripping time is 1.0～4.0h. After the addition, the temperature is 20～50. The stabilizer is prepared by the heat preservation reaction at ℃ for 0-3.0h, wherein the total amount of water used in this step is such that the mass concentration of the stabilizer is 5-40%, and the mass ratio of unsaturated fluorine-containing compound and acrylic acid is 1:1～3, the amount of the initiator is 0.5-3.5% of the total mass of the unsaturated fluorine-containing compound and acrylic acid, and the amount of the molecular weight regulator is 0.2-2.5% of the total mass of the unsaturated fluorine-containing compound and acrylic acid.
6. A high-strength solubilizing liquid accelerator according to claim 5, wherein the unsaturated fluorine-containing compound is 2-fluorocinnamic acid, 3-fluorocinnamic acid, 4-fluorocinnamic acid, 2- At least one of (trifluoromethyl) cinnamic acid, 3-(trifluoromethyl) cinnamic acid, and 4-(trifluoromethyl) cinnamic acid.
7. A high-strength solubilizing liquid accelerator according to claim 5, wherein the initiator is ammonium persulfate.
8. The high-strength solubilizing liquid quick-setting agent according to claim 5, wherein the molecular weight regulator is at least one of thioglycolic acid, mercaptopropionic acid and mercaptoethanol.
9. A high-strength solubilizing liquid quick-setting agent according to claim 1, wherein the pH value adjuster is concentrated sulfuric acid, p-toluenesulfonic acid, citric acid, tartaric acid, salicylic acid, oxalic acid, At least one of hydrofluoric acid.
10. A method for preparing a high-strength solubilizing liquid quick-setting agent, which is characterized in that: the preparation method includes the following steps: firstly, a stabilizer and water are added to a reaction kettle for stirring, and then a pH regulator is added and stirred evenly, Then add aluminum sulfate, aluminum citrate, hydroxyethyl cellulose and complexing enhancer separately and stir. After the materials are completely stirred and evenly mixed, the reaction is carried out at a temperature of 40-80°C for 1.0-4.0h, and the reaction is complete. The high-strength solubilizing liquid accelerator is obtained.