阅读说明：本技术 一种高强型高分子灌浆用固化剂及其制备工艺 (High-strength curing agent for polymer grouting and preparation process thereof ) 是由 潘巧珍 李丽坤 李娇 任嵬 于 2021-09-18 设计创作，主要内容包括：本发明公开一种高强型高分子灌浆用固化剂及其制备工艺,包括如下重量份原料：第一组分20-30份、第二组分23-25份、甲醛30-40份、三聚氰胺30-50份、去离子水50-60份、司盘200.1-0.3份；其制备工艺如下：第一步、制备第一组分和第二组分；第二步、将甲醛、三聚氰胺和去离子水混合均匀,得到混合液,调节混合液的pH值,设置温度为70-80℃,搅拌50-60min,得到预聚体溶液备用；第三步、将第一组分、第二组分和司盘20,室温搅拌5-10min,加入第二步制得的预聚体溶液,设置温度为60℃,调节反应液的pH值,搅拌2h,搅拌结束后调节体系pH值,得到一种高强型高分子灌浆用固化剂。(The invention discloses a high-strength curing agent for polymer grouting and a preparation process thereof, wherein the curing agent comprises the following raw materials in parts by weight: 20-30 parts of a first component, 23-25 parts of a second component, 30-40 parts of formaldehyde, 30-50 parts of melamine, 50-60 parts of deionized water and 200.1-0.3 part of span; the preparation process comprises the following steps: the method comprises the following steps of firstly, preparing a first component and a second component; step two, uniformly mixing formaldehyde, melamine and deionized water to obtain a mixed solution, adjusting the pH value of the mixed solution, setting the temperature to be 70-80 ℃, and stirring for 50-60min to obtain a prepolymer solution for later use; and thirdly, stirring the first component, the second component and span 20 at room temperature for 5-10min, adding the prepolymer solution prepared in the second step, setting the temperature to be 60 ℃, adjusting the pH value of the reaction solution, stirring for 2h, and adjusting the pH value of the system after stirring is finished to obtain the high-strength high-polymer grouting curing agent.)

1. The high-strength curing agent for polymer grouting is characterized by comprising the following raw materials in parts by weight: 20-30 parts of a first component, 23-25 parts of a second component, 30-40 parts of formaldehyde, 30-50 parts of melamine, 50-60 parts of deionized water and 200.1-0.3 part of span;

the high-strength polymer curing agent for grouting is prepared by the following steps:

the method comprises the following steps of firstly, preparing a first component and a second component;

secondly, adding formaldehyde, melamine and deionized water into a reaction kettle, uniformly mixing to obtain a mixed solution, adjusting the pH value of the mixed solution to 9-10 by using sodium hydroxide, setting the temperature to 70-80 ℃ and the rotating speed to 300r/min, and stirring for 50-60min to obtain a prepolymer solution for later use;

thirdly, mixing the first component, the second component and span 20; stirring at room temperature for 5-10min under the condition of the rotating speed of 1000r/min, adding the prepolymer solution prepared in the second step, setting the temperature to be 60 ℃, adjusting the pH value of the reaction solution to be 4-5 by using 1mol/L hydrochloric acid solution, stirring for 2h under the condition of the rotating speed of 500r/min, and adjusting the pH value of a system to be 7 by using sodium hydroxide after the stirring is finished to obtain the high-strength high-polymer grouting curing agent.

2. The curing agent for high-strength polymer grouting according to claim 1, wherein the first component is prepared by the following steps:

step S11, adding soybean oil and span 80 into a round-bottom flask, setting the temperature at 50-60 ℃ and the rotating speed at 300r/min, stirring for 20-30min, then adding a chitosan solution, keeping the temperature and the rotating speed unchanged, and continuing stirring for 1h to obtain a pre-emulsion;

and step S12, adding a cross-linking agent into the obtained pre-emulsion, stirring for 3 hours at the temperature of 40 ℃ and the rotating speed of 300r/min, centrifuging the obtained reaction liquid at the rotating speed of 3000r/min for 10 minutes, removing supernatant, carrying out vacuum filtration on the obtained mixed liquid, washing with ethyl acetate, and drying the obtained filter cake to constant weight at the temperature of 40 ℃ under vacuum conditions to obtain the first component.

3. The high-strength polymer grouting curing agent as claimed in claim 2, wherein in step S11, the chitosan solution is prepared by mixing chitosan and 1% volume fraction acetic acid aqueous solution in a mass-to-volume ratio of 2 g: 100mL, wherein the dosage ratio of the soybean oil, the span 80 and the chitosan solution is 7 mL: 0.5 g: 3-5 mL; the cross-linking agent in the step S12 is the mixture of genipin and vanillin with equal volume; the volume of the pre-emulsion and the cross-linking agent is 10-12: 2.

4. the curing agent for high-strength polymer grouting according to claim 1, wherein the second component is prepared by the following steps:

step S21, adding sebacic acid, itaconic acid and diethylenetriamine into a three-neck flask, setting the temperature at 100 ℃ and the rotating speed at 200r/min, stirring for 10 hours under the protection of nitrogen, then increasing the temperature to 160 ℃, keeping the rotating speed constant, continuing to stir for 20 hours, decreasing the temperature to 80 ℃, adding acrylamide, continuing to stir, adding an ammonium persulfate aqueous solution while stirring, after the addition is finished, keeping the temperature constant, continuing to stir for 7 hours, then increasing the temperature to 120 ℃, adding carbamide, continuing to react, increasing the temperature to 5 ℃ every 1 hour, keeping the temperature constant when the temperature increases to 160 ℃, continuing to stir for 2 hours, uniformly mixing the obtained reaction liquid and deionized water in equal volume, standing for 20 hours after mixing, performing vacuum filtration, and drying the obtained filter cake to constant weight at 80 ℃ under the vacuum condition to obtain a mixture a;

step S22, adding 2-ethyl-4-methylimidazole, deionized water and maleic acid into a four-neck flask, heating and stirring for 2-3h under the conditions that the temperature is 100-102 ℃ and the rotating speed is 200r/min, and cooling the reaction liquid to room temperature after stirring to obtain modified imidazole;

step S23, mixing the modified imidazole, the adipic dihydrazide and the mixture a according to the mass ratio of 1: 7: 25 and reacting at 80 ℃ for 5 hours to obtain a second component.

5. The curing agent according to claim 4, wherein the molar ratio of sebacic acid, itaconic acid, diethylenetriamine and acrylamide in step S21 is 8: 2: 0.5-0.7: 0.2-0.4; the mass fraction of the ammonium persulfate aqueous solution is 10 percent; the amount of the carbamide accounts for 10-30% of the total mass of the sebacic acid, the itaconic acid, the diethylenetriamine and the acrylamide; in the step S22, the dosage ratio of the 2-ethyl-4-methylimidazole to the deionized water to the maleic acid is 3 g: 70-72 mL: 4-6 g.

6. The preparation process of the high-strength polymer grouting curing agent according to claim 1, characterized by comprising the following steps:

the method comprises the following steps of firstly, preparing a first component and a second component;

secondly, adding formaldehyde, melamine and deionized water into a reaction kettle, uniformly mixing to obtain a mixed solution, adjusting the pH value of the mixed solution to 9-10 by using sodium hydroxide, setting the temperature to 70-80 ℃ and the rotating speed to 300r/min, and stirring for 50-60min to obtain a prepolymer solution for later use;

thirdly, mixing the first component, the second component and span 20; stirring at room temperature for 5-10min under the condition of the rotating speed of 1000r/min, adding the prepolymer solution prepared in the second step, setting the temperature to be 60 ℃, adjusting the pH value of the reaction solution to be 4-5 by using 1mol/L hydrochloric acid solution, stirring for 2h under the condition of the rotating speed of 500r/min, and adjusting the pH value of a system to be 7 by using sodium hydroxide after the stirring is finished to obtain the high-strength high-polymer grouting curing agent.

Technical Field

The invention belongs to the technical field of curing agents, and particularly relates to a high-strength curing agent for polymer grouting and a preparation process thereof.

Background

Currently, epoxy grouting materials widely used in the chemical grouting industry are epoxy-furfural-acetone systems. In this system, epoxy resins are generally used for bonding objects; and curing agents are used to cure the epoxy resin. Epoxy resins with viscosities as high as thousands or even tens of thousands have a very low viscosity, as low as a dozen or even a few mpa · s, due to the dilution effect of furfural and acetone. When using such low viscosity epoxy resins as epoxy grouting materials, the viscosity requirement becomes less important in selecting the corresponding curing agent, because the viscosity of the curing agent is diluted when the epoxy resin is mixed with the curing agent before grouting. Currently, epoxy grouting material curing agents selected in the industry are generally modified amines, and the viscosity is generally thousands or hundreds of mpa · s.

However, in the case of the environment-friendly epoxy grouting material, the solvent cannot be added to the environment-friendly epoxy grouting material too much, so that the viscosity of the epoxy grouting material is generally high and is at least several tens of mpa · s. This results in a complicated selection of a curing agent for the epoxy grouting material corresponding thereto;

because of the high viscosity of epoxy resins, the viscosity of the curing agent is required to be low. At the same time, since there is no dilution by the solvent, the reaction becomes faster during mixing, thus risking implosion.

Disclosure of Invention

In order to overcome the technical problems, the invention provides a high-strength curing agent for polymer grouting and a preparation process thereof.

The technical problems to be solved by the invention are as follows:

the curing agent not only plays a role in dilution, but also cannot have a risk of sudden aggregation; meanwhile, the adhesive also requires high compression strength, tensile strength and bonding strength, good curing property under water and at low temperature, and stable storage.

The purpose of the invention can be realized by the following technical scheme:

a high-strength high-polymer grouting curing agent comprises the following raw materials in parts by weight: 20-30 parts of a first component, 23-25 parts of a second component, 30-40 parts of formaldehyde, 30-50 parts of melamine, 50-60 parts of deionized water and 200.1-0.3 part of span;

the high-strength polymer curing agent for grouting is prepared by the following steps:

the method comprises the following steps of firstly, preparing a first component and a second component;

secondly, adding formaldehyde, melamine and deionized water into a reaction kettle, uniformly mixing to obtain a mixed solution, adjusting the pH value of the mixed solution to 9-10 by using sodium hydroxide, setting the temperature to 70-80 ℃ and the rotating speed to 300r/min, and stirring for 50-60min to obtain a prepolymer solution for later use;

thirdly, mixing the first component, the second component and span 20; stirring at room temperature for 5-10min under the condition of the rotating speed of 1000r/min, adding the prepolymer solution prepared in the second step, setting the temperature to be 60 ℃, adjusting the pH value of the reaction solution to be 4-5 by using 1mol/L hydrochloric acid solution, stirring for 2h under the condition of the rotating speed of 500r/min, and adjusting the pH value of a system to be 7 by using sodium hydroxide after the stirring is finished to obtain the high-strength high-polymer grouting curing agent.

The first component is loaded with the second component, i.e., the cured ingredients are encapsulated within the chitosan microspheres. The melamine and formaldehyde prepolymer solution is used as a capsule wall, the melamine and formaldehyde form a reaction to form a microcapsule, the generated microcapsule has a stable three-dimensional crosslinking structure and good slow release performance, the capsule wall coats the first component and the second component, the prepared curing agent slowly releases the first component and the second component in high-strength polymer grouting to prevent sudden aggregation, and a crosslinking network of a mixture a in the second component can reinforce the construction defect, so that the construction efficiency is improved.

Further, the first component is prepared by the following steps:

step S11, adding soybean oil and span 80 into a round-bottom flask, setting the temperature at 50-60 ℃ and the rotating speed at 300r/min, stirring for 20-30min, then adding a chitosan solution, keeping the temperature and the rotating speed unchanged, and continuing stirring for 1h to obtain a pre-emulsion;

and step S12, adding a cross-linking agent into the obtained pre-emulsion, stirring for 3 hours at the temperature of 40 ℃ and the rotating speed of 300r/min, centrifuging the obtained reaction liquid at the rotating speed of 3000r/min for 10 minutes, removing supernatant, carrying out vacuum filtration on the obtained mixed liquid, washing with ethyl acetate, and drying the obtained filter cake to constant weight at the temperature of 40 ℃ under vacuum conditions to obtain the first component.

Further, in step S11, the chitosan solution is prepared by mixing chitosan and 1% volume fraction acetic acid aqueous solution in a mass-to-volume ratio of 2 g: 100mL, wherein the dosage ratio of the soybean oil, the span 80 and the chitosan solution is 7 mL: 0.5 g: 3-5 mL; the cross-linking agent in the step S12 is the mixture of genipin and vanillin with equal volume; the volume of the pre-emulsion and the cross-linking agent is 10-12: 2.

the prepared first component is chitosan microspheres, the particle size distribution is 15-20 mu m, and genipin and vanillin are used as a compound cross-linking agent, so that the prepared microspheres have good dispersibility and more uniform particle size.

Further, the second component is prepared by the following steps:

step S21, adding sebacic acid, itaconic acid and diethylenetriamine into a three-neck flask, setting the temperature at 100 ℃ and the rotating speed at 200r/min, stirring for 10 hours under the protection of nitrogen, then increasing the temperature to 160 ℃, keeping the rotating speed constant, continuing to stir for 20 hours, decreasing the temperature to 80 ℃, adding acrylamide, continuing to stir, adding an ammonium persulfate aqueous solution while stirring, after the addition is finished, keeping the temperature constant, continuing to stir for 7 hours, then increasing the temperature to 120 ℃, adding carbamide, continuing to react, increasing the temperature to 5 ℃ every 1 hour, keeping the temperature constant when the temperature increases to 160 ℃, continuing to stir for 2 hours, uniformly mixing the obtained reaction liquid and deionized water in equal volume, standing for 20 hours after mixing, performing vacuum filtration, and drying the obtained filter cake to constant weight at 80 ℃ under the vacuum condition to obtain a mixture a;

sebacic acid, itaconic acid and diethylenetriamine firstly react to generate a linear low-molecular-weight amide polycondensate, then the polycondensate and acrylamide and carbamide generate free radical copolymerization reaction under the action of initiator ammonium persulfate to generate chemical crosslinking, the sebacic acid, itaconic acid and other biomolecular acids are selected as reaction raw materials, hydrogen bond groups are introduced, a mixture a generated by the reaction contains hydrogen bonds, double bonds contained in the itaconic acid can also form covalent crosslinking to a certain degree, and the obtained mixture a contains a three-dimensional network structure with covalent and non-covalent functions.

Step S22, adding 2-ethyl-4-methylimidazole, deionized water and maleic acid into a four-neck flask, heating and stirring for 2-3h under the conditions that the temperature is 100-102 ℃ and the rotating speed is 200r/min, and cooling the reaction liquid to room temperature after stirring to obtain modified imidazole;

step S23, mixing the modified imidazole, the adipic dihydrazide and the mixture a according to the mass ratio of 1: 7: 25 and reacting at 80 ℃ for 5 hours to obtain a second component.

Further, in step S21, the molar ratio of sebacic acid, itaconic acid, diethylenetriamine and acrylamide is 8: 2: 0.5-0.7: 0.2-0.4; the mass fraction of the ammonium persulfate aqueous solution is 10 percent; the amount of the carbamide accounts for 10-30% of the total mass of the sebacic acid, the itaconic acid, the diethylenetriamine and the acrylamide; in the step S22, the dosage ratio of the 2-ethyl-4-methylimidazole to the deionized water to the maleic acid is 3 g: 70-72 mL: 4-6 g.

The imidazole reacts with maleic acid to prepare modified imidazole, which has an accelerating effect on curing with an epoxy system, adipyl is a latent curing component, adipyl can be used as a cross-linking agent of the modified imidazole and the mixture a, the prepared second component can accelerate curing, and primary amino groups and amide groups in the mixture a are easy to combine with the epoxy component and can be cured at normal temperature.

Further, the preparation process of the high-strength curing agent for polymer grouting comprises the following steps:

the method comprises the following steps of firstly, preparing a first component and a second component;

secondly, adding formaldehyde, melamine and deionized water into a reaction kettle, uniformly mixing to obtain a mixed solution, adjusting the pH value of the mixed solution to 9-10 by using sodium hydroxide, setting the temperature to 70-80 ℃ and the rotating speed to 300r/min, and stirring for 50-60min to obtain a prepolymer solution for later use;

thirdly, mixing the first component, the second component and span 20; stirring at room temperature for 5-10min under the condition of the rotating speed of 1000r/min, adding the prepolymer solution prepared in the second step, setting the temperature to be 60 ℃, adjusting the pH value of the reaction solution to be 4-5 by using 1mol/L hydrochloric acid solution, stirring for 2h under the condition of the rotating speed of 500r/min, and adjusting the pH value of a system to be 7 by using sodium hydroxide after the stirring is finished to obtain the high-strength high-polymer grouting curing agent.

The invention has the beneficial effects that:

the prepared first component is chitosan microspheres, the particle size distribution is 15-20 mu m, and genipin and vanillin are used as a compound cross-linking agent, so that the prepared microspheres have good dispersibility and more uniform particle size. In the process of preparing the second component, sebacic acid, itaconic acid and diethylenetriamine firstly react to generate a linear low-molecular-weight amide polycondensate, then the linear low-molecular-weight amide polycondensate and acrylamide and carbamide generate a free radical copolymerization reaction under the action of an initiator ammonium persulfate to generate chemical crosslinking, the sebacic acid, itaconic acid and other biomolecular acids are selected as reaction raw materials, a hydrogen bond group is introduced, a mixture a generated by the reaction contains a hydrogen bond, double bonds contained in the itaconic acid can also form covalent crosslinking to a certain degree, and the obtained mixture a contains a three-dimensional network structure with covalent and non-covalent functions. The imidazole reacts with maleic acid to prepare modified imidazole, which has an accelerating effect on curing with an epoxy system, adipyl is a latent curing component, adipyl can be used as a cross-linking agent of the modified imidazole and the mixture a, the prepared second component can accelerate curing, and primary amino groups and amide groups in the mixture a are easy to combine with the epoxy component and can be cured at normal temperature.

The first component is loaded with the second component, i.e., the cured ingredients are encapsulated within the chitosan microspheres. The melamine and formaldehyde prepolymer solution is used as a capsule wall, the melamine and formaldehyde form a reaction to form a microcapsule, the generated microcapsule has a stable three-dimensional crosslinking structure and good slow release performance, the capsule wall coats the first component and the second component, the prepared curing agent slowly releases the first component and the second component in high-strength polymer grouting to prevent sudden aggregation, and a crosslinking network of a mixture a in the second component can reinforce the construction defect, so that the construction efficiency is improved.

Detailed Description

The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the 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

A high-strength high-polymer grouting curing agent comprises the following raw materials in parts by weight: 20 parts of a first component, 23 parts of a second component, 30 parts of formaldehyde, 30 parts of melamine, 50 parts of deionized water and 200.1 parts of span;

the high-strength polymer curing agent for grouting is prepared by the following steps:

the method comprises the following steps of firstly, preparing a first component and a second component;

secondly, adding formaldehyde, melamine and deionized water into a reaction kettle, uniformly mixing to obtain a mixed solution, adjusting the pH value of the mixed solution to 9 by using sodium hydroxide, setting the temperature to be 70 ℃ and the rotating speed to be 300r/min, and stirring for 50min to obtain a prepolymer solution for later use;

thirdly, mixing the first component, the second component and span 20; stirring at room temperature for 5min under the condition of the rotating speed of 1000r/min, adding the prepolymer solution prepared in the second step, setting the temperature to be 60 ℃, adjusting the pH value of the reaction solution to be 4 by using 1mol/L hydrochloric acid solution, stirring for 2h under the condition of the rotating speed of 500r/min, and adjusting the pH value of a system to be 7 by using sodium hydroxide after the stirring is finished, thereby obtaining the high-strength polymer grouting curing agent.

Wherein the first component is prepared by the following steps:

step S11, adding soybean oil and span 80 into a round-bottom flask, setting the temperature at 50 ℃ and the rotating speed at 300r/min, stirring for 20min, then adding a chitosan solution, keeping the temperature and the rotating speed unchanged, and continuing stirring for 1h to obtain a pre-emulsion;

and step S12, adding a cross-linking agent into the obtained pre-emulsion, stirring for 3 hours at the temperature of 40 ℃ and the rotating speed of 300r/min, centrifuging the obtained reaction liquid at the rotating speed of 3000r/min for 10 minutes, removing supernatant, carrying out vacuum filtration on the obtained mixed liquid, washing with ethyl acetate, and drying the obtained filter cake to constant weight at the temperature of 40 ℃ under vacuum conditions to obtain the first component.

In step S11, the chitosan solution is prepared by mixing chitosan and 1% volume fraction acetic acid aqueous solution in a mass-to-volume ratio of 2 g: 100mL, wherein the dosage ratio of the soybean oil, the span 80 and the chitosan solution is 7 mL: 0.5 g: 3 mL; the cross-linking agent in the step S12 is the mixture of genipin and vanillin with equal volume; the volume of pre-emulsion and crosslinker was 10: 2.

wherein the second component is prepared by the following steps:

step S21, adding sebacic acid, itaconic acid and diethylenetriamine into a three-neck flask, setting the temperature at 100 ℃ and the rotating speed at 200r/min, stirring for 10 hours under the protection of nitrogen, then increasing the temperature to 160 ℃, keeping the rotating speed constant, continuing to stir for 20 hours, decreasing the temperature to 80 ℃, adding acrylamide, continuing to stir, adding an ammonium persulfate aqueous solution while stirring, after the addition is finished, keeping the temperature constant, continuing to stir for 7 hours, then increasing the temperature to 120 ℃, adding carbamide, continuing to react, increasing the temperature to 5 ℃ every 1 hour, keeping the temperature constant when the temperature increases to 160 ℃, continuing to stir for 2 hours, uniformly mixing the obtained reaction liquid and deionized water in equal volume, standing for 20 hours after mixing, performing vacuum filtration, and drying the obtained filter cake to constant weight at 80 ℃ under the vacuum condition to obtain a mixture a;

step S22, adding 2-ethyl-4-methylimidazole, deionized water and maleic acid into a four-neck flask, heating and stirring for 2 hours at the temperature of 100 ℃ and the rotating speed of 200r/min, and cooling the reaction liquid to room temperature after stirring to obtain modified imidazole;

step S23, mixing the modified imidazole, the adipic dihydrazide and the mixture a according to the mass ratio of 1: 7: 25 and reacting at 80 ℃ for 5 hours to obtain a second component.

Wherein, in the step S21, the molar ratio of sebacic acid, itaconic acid, diethylenetriamine and acrylamide is 8: 2: 0.5: 0.2; the mass fraction of the ammonium persulfate aqueous solution is 10 percent; the using amount of the carbamide is 10 percent of the total mass of the sebacic acid, the itaconic acid, the diethylenetriamine and the acrylamide; in the step S22, the dosage ratio of the 2-ethyl-4-methylimidazole to the deionized water to the maleic acid is 3 g: 70mL of: 4g of the total weight.

Example 2

A high-strength high-polymer grouting curing agent comprises the following raw materials in parts by weight: 20-30 parts of a first component, 24 parts of a second component, 35 parts of formaldehyde, 40 parts of melamine, 55 parts of deionized water and 200.2 parts of span;

the high-strength polymer curing agent for grouting is prepared by the following steps:

the method comprises the following steps of firstly, preparing a first component and a second component;

secondly, adding formaldehyde, melamine and deionized water into a reaction kettle, uniformly mixing to obtain a mixed solution, adjusting the pH value of the mixed solution to 9 by using sodium hydroxide, setting the temperature to be 75 ℃ and the rotating speed to be 300r/min, and stirring for 55min to obtain a prepolymer solution for later use;

thirdly, mixing the first component, the second component and span 20; stirring for 8min at room temperature under the condition of the rotating speed of 1000r/min, adding the prepolymer solution prepared in the second step, setting the temperature to be 60 ℃, adjusting the pH value of the reaction solution to be 4 by using 1mol/L hydrochloric acid solution, stirring for 2h under the condition of the rotating speed of 500r/min, and adjusting the pH value of a system to be 7 by using sodium hydroxide after the stirring is finished, thereby obtaining the high-strength polymer grouting curing agent.

Wherein the first component is prepared by the following steps:

step S11, adding soybean oil and span 80 into a round-bottom flask, setting the temperature at 55 ℃ and the rotating speed at 300r/min, stirring for 25min, then adding a chitosan solution, keeping the temperature and the rotating speed unchanged, and continuing stirring for 1h to obtain a pre-emulsion;

and step S12, adding a cross-linking agent into the obtained pre-emulsion, stirring for 3 hours at the temperature of 40 ℃ and the rotating speed of 300r/min, centrifuging the obtained reaction liquid at the rotating speed of 3000r/min for 10 minutes, removing supernatant, carrying out vacuum filtration on the obtained mixed liquid, washing with ethyl acetate, and drying the obtained filter cake to constant weight at the temperature of 40 ℃ under vacuum conditions to obtain the first component.

In step S11, the chitosan solution is prepared by mixing chitosan and 1% volume fraction acetic acid aqueous solution in a mass-to-volume ratio of 2 g: 100mL, wherein the dosage ratio of the soybean oil, the span 80 and the chitosan solution is 7 mL: 0.5 g: 4 mL; the cross-linking agent in the step S12 is the mixture of genipin and vanillin with equal volume; the volume of pre-emulsion and crosslinker was 11: 2.

wherein the second component is prepared by the following steps:

step S21, adding sebacic acid, itaconic acid and diethylenetriamine into a three-neck flask, setting the temperature at 110 ℃ and the rotating speed at 200r/min, stirring for 10 hours under the protection of nitrogen, then increasing the temperature to 160 ℃, keeping the rotating speed constant, continuing to stir for 20 hours, decreasing the temperature to 80 ℃, adding acrylamide, continuing to stir, adding an ammonium persulfate aqueous solution while stirring, after the addition is finished, keeping the temperature constant, continuing to stir for 7 hours, then increasing the temperature to 120 ℃, adding carbamide, continuing to react, increasing the temperature for 5 ℃ every 1 hour, keeping the temperature constant when the temperature is 160 ℃, continuing to stir for 2 hours, uniformly mixing the obtained reaction liquid and deionized water in equal volume, standing for 20 hours after mixing, performing suction filtration under reduced pressure, and drying the obtained filter cake to constant weight under the vacuum condition at 80 ℃ to obtain a mixture a;

step S22, adding 2-ethyl-4-methylimidazole, deionized water and maleic acid into a four-neck flask, heating and stirring for 2 hours at the temperature of 101 ℃ and the rotating speed of 200r/min, and cooling the reaction liquid to room temperature after stirring to obtain modified imidazole;

step S23, mixing the modified imidazole, the adipic dihydrazide and the mixture a according to the mass ratio of 1: 7: 25 and reacting at 80 ℃ for 5 hours to obtain a second component.

Wherein, in the step S21, the molar ratio of sebacic acid, itaconic acid, diethylenetriamine and acrylamide is 8: 2: 0.6: 0.3; the mass fraction of the ammonium persulfate aqueous solution is 10 percent; the using amount of the carbamide is 20 percent of the total mass of the sebacic acid, the itaconic acid, the diethylenetriamine and the acrylamide; in the step S22, the dosage ratio of the 2-ethyl-4-methylimidazole to the deionized water to the maleic acid is 3 g: 71 mL: 5g of the total weight.

Example 3

A high-strength high-polymer grouting curing agent comprises the following raw materials in parts by weight: 30 parts of a first component, 25 parts of a second component, 40 parts of formaldehyde, 50 parts of melamine, 60 parts of deionized water and 200.3 parts of span;

the high-strength polymer curing agent for grouting is prepared by the following steps:

the method comprises the following steps of firstly, preparing a first component and a second component;

secondly, adding formaldehyde, melamine and deionized water into a reaction kettle, uniformly mixing to obtain a mixed solution, adjusting the pH value of the mixed solution to 10 by using sodium hydroxide, setting the temperature to 80 ℃ and the rotating speed to 300r/min, and stirring for 60min to obtain a prepolymer solution for later use;

thirdly, mixing the first component, the second component and span 20; stirring at room temperature for 10min under the condition of the rotating speed of 1000r/min, adding the prepolymer solution prepared in the second step, setting the temperature to be 60 ℃, adjusting the pH value of the reaction solution to be 5 by using 1mol/L hydrochloric acid solution, stirring for 2h under the condition of the rotating speed of 500r/min, and adjusting the pH value of a system to be 7 by using sodium hydroxide after the stirring is finished, thereby obtaining the high-strength polymer grouting curing agent.

Wherein the first component is prepared by the following steps:

step S11, adding soybean oil and span 80 into a round-bottom flask, setting the temperature at 60 ℃ and the rotating speed at 300r/min, stirring for 30min, then adding a chitosan solution, keeping the temperature and the rotating speed unchanged, and continuing stirring for 1h to obtain a pre-emulsion;

and step S12, adding a cross-linking agent into the obtained pre-emulsion, stirring for 3 hours at the temperature of 40 ℃ and the rotating speed of 300r/min, centrifuging the obtained reaction liquid at the rotating speed of 3000r/min for 10 minutes, removing supernatant, carrying out vacuum filtration on the obtained mixed liquid, washing with ethyl acetate, and drying the obtained filter cake to constant weight at the temperature of 40 ℃ under vacuum conditions to obtain the first component.

In step S11, the chitosan solution is prepared by mixing chitosan and 1% volume fraction acetic acid aqueous solution in a mass-to-volume ratio of 2 g: 100mL, wherein the dosage ratio of the soybean oil, the span 80 and the chitosan solution is 7 mL: 0.5 g: 5 mL; the cross-linking agent in the step S12 is the mixture of genipin and vanillin with equal volume; the volume of pre-emulsion and crosslinker was 12: 2.

wherein the second component is prepared by the following steps:

step S21, adding sebacic acid, itaconic acid and diethylenetriamine into a three-neck flask, setting the temperature at 120 ℃ and the rotating speed at 200r/min, stirring for 10 hours under the protection of nitrogen, then increasing the temperature to 160 ℃, keeping the rotating speed constant, continuing to stir for 20 hours, decreasing the temperature to 80 ℃, adding acrylamide, continuing to stir, adding an ammonium persulfate aqueous solution while stirring, after the addition is finished, keeping the temperature constant, continuing to stir for 7 hours, then increasing the temperature to 120 ℃, adding carbamide, continuing to react, increasing the temperature for 5 ℃ every 1 hour, keeping the temperature constant when the temperature is 160 ℃, continuing to stir for 2 hours, uniformly mixing the obtained reaction liquid and deionized water in equal volume, standing for 20 hours after mixing, performing suction filtration under reduced pressure, and drying the obtained filter cake to constant weight under the vacuum condition at 80 ℃ to obtain a mixture a;

step S22, adding 2-ethyl-4-methylimidazole, deionized water and maleic acid into a four-neck flask, heating and stirring for 3 hours at the temperature of 102 ℃ and the rotation speed of 200r/min, and cooling the reaction liquid to room temperature after stirring to obtain modified imidazole;

step S23, mixing the modified imidazole, the adipic dihydrazide and the mixture a according to the mass ratio of 1: 7: 25 and reacting at 80 ℃ for 5 hours to obtain a second component.

Wherein, in the step S21, the molar ratio of sebacic acid, itaconic acid, diethylenetriamine and acrylamide is 8: 2: 0.7: 0.4; the mass fraction of the ammonium persulfate aqueous solution is 10 percent; the using amount of the carbamide is 30 percent of the total mass of the sebacic acid, the itaconic acid, the diethylenetriamine and the acrylamide; in the step S22, the dosage ratio of the 2-ethyl-4-methylimidazole to the deionized water to the maleic acid is 3 g: 72 mL: 6 g.

Comparative example 1

The comparative example is a common high-strength polymer grouting curing agent in the market.

The performance of the curing agent prepared in examples 1-3 and the curing agent prepared in comparative example 1 was tested, and the performance of the slurry was tested when the addition amount of the curing agent was 20%, wherein the slurry was a commonly used epoxy resin material; the test results are shown in table 1 below:

TABLE 1

From the above table 1, it can be seen that both the curing agent itself and the prepared slurry have a viscosity value of not more than 30mpa.s, which meets the low viscosity requirement in the chemical grouting field, and the prepared curing agent has better compressive strength, tensile strength and bonding strength after being added into the slurry compared with the existing curing agent, i.e. the high-strength curing agent for polymer grouting prepared by the invention has better curing performance and is suitable for long-term stable storage.

In the description herein, references to the description of "one embodiment," "an example," "a specific example" or the like are intended to mean that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the invention. In this specification, the schematic representations of the terms used above do not necessarily refer to the same embodiment or example. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples.

The foregoing is illustrative and explanatory only and is not intended to be exhaustive or to limit the invention to the precise embodiments described, and various modifications, additions, and substitutions may be made by those skilled in the art without departing from the scope of the invention or exceeding the scope of the claims.