阅读说明：本技术 一种用于水下灌注浆材料的水下抗分散剂的制备方法 (Preparation method of underwater anti-dispersant for underwater grouting slurry material ) 是由 时磊 沈焱 毛荣良 于 2021-08-26 设计创作，主要内容包括：本发明公开了一种用于水下灌注浆材料的水下抗分散剂的制备方法,包括步骤为：向加热的羧甲基纤维素钠和水的混合液中加入过硫酸氢钠和对苯乙烯磺酸钠,反应后再加入过硫酸氢钠、甲基烯丙基聚氧乙烯醚,反应得到改性羧甲基纤维素钠聚合物溶液；向加热的水中加入硬脂酸搅拌,再加入碳搅拌,最后加入氢氧化钠,降温加入碳酸钙,待反应完全后冷却加入氨水搅拌,得到乳白色粘稠状液体；混合淀粉醚、硬脂酸、聚乙烯醇、十二烷基苯磺酸钠和马来酰亚胺水溶液,得到混合液；将混合液与水混合并加热,再一边滴加改性羧甲基纤维素钠聚合物溶液,另一边滴加乳白色粘稠状液体,加入结束后滴加甲酸钙水溶液,反应后用氢氧化钠中和得到水下抗分散剂性能优异。(The invention discloses a preparation method of an underwater anti-dispersant for underwater grouting materials, which comprises the following steps: adding sodium hydrogen persulfate and sodium p-styrene sulfonate into a heated mixed solution of sodium carboxymethylcellulose and water, reacting, then adding sodium hydrogen persulfate and methallyl polyoxyethylene ether, and reacting to obtain a modified sodium carboxymethylcellulose polymer solution; adding stearic acid into heated water, stirring, adding carbon, stirring, finally adding sodium hydroxide, cooling, adding calcium carbonate, cooling after complete reaction, adding ammonia water, and stirring to obtain a milky viscous liquid; mixing starch ether, stearic acid, polyvinyl alcohol, sodium dodecyl benzene sulfonate and maleimide aqueous solution to obtain a mixed solution; and mixing the mixed solution with water, heating, dropwise adding the modified sodium carboxymethylcellulose polymer solution on one side, dropwise adding the milky viscous liquid on the other side, dropwise adding the calcium formate aqueous solution after the addition is finished, and neutralizing with sodium hydroxide after the reaction to obtain the underwater anti-dispersant with excellent performance.)

1. A preparation method of an underwater anti-dispersant for underwater grouting materials is characterized by comprising the following steps:

(1) adding sodium hydrogen persulfate and sodium p-styrene sulfonate into a heated mixed solution of sodium carboxymethylcellulose and water, reacting, then adding sodium hydrogen persulfate and methallyl polyoxyethylene ether, and reacting to obtain a modified sodium carboxymethylcellulose polymer solution;

(2) adding stearic acid into heated water, stirring, adding carbon, stirring, finally adding sodium hydroxide, cooling, adding calcium carbonate, cooling after complete reaction, adding ammonia water, and stirring to obtain a milky viscous liquid;

(3) mixing starch ether, stearic acid, polyvinyl alcohol, sodium dodecyl benzene sulfonate and maleimide aqueous solution to obtain a mixed solution;

(4) and (3) mixing the mixed solution obtained in the step (3) with water, heating, dropwise adding the modified sodium carboxymethyl cellulose polymer solution obtained in the step (1) on one side, dropwise adding the milky viscous liquid obtained in the step (2) on the other side, dropwise adding a calcium formate aqueous solution after the addition is finished, and neutralizing with sodium hydroxide after reaction to obtain the underwater anti-dispersant for the underwater grouting slurry material.

2. The preparation method according to claim 1, wherein the modified sodium carboxymethyl cellulose polymer solution prepared in step (1) comprises the following raw materials: adding 0.05-0.15 part of sodium hydrogen persulfate and 0.5-2 parts of sodium p-styrene sulfonate into a heated mixed solution of 3-5 parts of sodium carboxymethylcellulose and 25-35 parts of water, reacting, then adding 0.05-0.15 part of sodium hydrogen persulfate and 0.05-0.15 part of methyl allyl polyoxyethylene ether, and reacting to obtain a modified sodium carboxymethylcellulose polymer solution with the mass fraction of 25-35%.

3. The preparation method according to claim 1, wherein the heating temperature in the heated mixed solution of sodium carboxymethylcellulose and water in the step (1) is 60-80 ℃; adding sodium hydrogen persulfate and sodium p-styrene sulfonate, and reacting for 25-40 min; adding the methyl allyl polyoxyethylene ether, and then keeping the temperature for reaction for 0.5-1.5 hours.

4. The method according to claim 1, wherein the methallyl polyoxyethylene ether is added dropwise in step (1) for 25 to 40 minutes.

5. The method according to claim 1, wherein the milky viscous liquid obtained in step (2) contains the following raw materials: adding 1-3 parts of stearic acid into 250 parts of heated 150-one water, stirring, adding 2-4 parts of carbon, stirring, finally adding 5-8 parts of sodium hydroxide, cooling, adding 6-8 parts of calcium carbonate, cooling after complete reaction, adding 28-32 parts of ammonia water, and stirring to obtain a milky viscous liquid.

6. The method according to claim 1, wherein the temperature of the water in the step (2) is 45 to 55 ℃; adding sodium hydroxide, and cooling to 28-33 deg.C; the temperature to which the calcium carbonate is cooled after addition is 18-22 ℃.

7. The process according to claim 1, wherein the stearic acid is added in the step (2) and then stirred for 0.5 to 2 minutes; adding carbon and stirring for 0.3-1 min; adding ammonia water and stirring for 1-3 min.

8. The method according to claim 1, wherein the mixed solution in the step (3) comprises the following components: 1-3 parts of starch ether, 5-7 parts of stearic acid, 2-4 parts of polyvinyl alcohol, 5-7 parts of sodium dodecyl benzene sulfonate and 9-11 parts of maleimide aqueous solution by mass; the mass fraction of the maleimide aqueous solution is 4-6% of maleimide aqueous solution.

9. The preparation method according to claim 1, wherein the specific steps in the step (4) are as follows: and (3) mixing and heating 20 parts of mixed solution obtained in the step (3) with 18-23 parts of water, dropwise adding 5-8 parts of modified sodium carboxymethyl cellulose polymer solution obtained in the step (1) on one side, dropwise adding 5-8 parts of milky viscous liquid obtained in the step (2) on the other side, finally dropwise adding 6-10 parts of calcium formate aqueous solution after the addition is finished, and neutralizing with sodium hydroxide after reaction to obtain the underwater anti-dispersing agent for the underwater grouting slurry material.

10. The method according to claim 1, wherein the mixture in step (4) is mixed with water and then heated to 75-85 ℃; the dropping time of the modified sodium carboxymethyl cellulose polymer solution and the milky viscous liquid is 4.5 to 6 hours; the calcium formate aqueous solution is 9-11% by mass; the dropping time of the calcium formate aqueous solution is 80-100min, and the temperature is kept for 2-3 hours after the dropping is finished; the pH was neutralized to 7 with sodium hydroxide.

Technical Field

The invention relates to the technical field of building materials, in particular to a preparation method of an underwater anti-dispersing agent for underwater grouting materials.

Background

The cement-based grouting material is a powdery material prepared by premixing a high-strength cementing component, a super-inking component, an expansion component, a preferred graded aggregate component and a trace amount of modification component in a factory according to a proper proportion. When in use, the self-leveling high-strength non-shrinkage grouting material can be prepared by adding water and stirring, has uniform and proper consistency, and can meet the construction requirements. Conventional cement-based grouting materials, including concrete, grouting materials, cement paste and the like, are difficult to normally use in special environments and conditions or during construction of special parts.

Disclosure of Invention

The invention mainly solves the technical problem of providing a preparation method of an underwater anti-dispersant for an underwater grouting material, and the obtained underwater anti-dispersant is specially applied to a cement-based grouting material needing to be constructed in an underwater environment and can be produced and applied in the market.

In order to solve the technical problems, the invention adopts a technical scheme that: the preparation method of the underwater anti-dispersing agent for the underwater grouting material comprises the following steps:

(1) adding sodium hydrogen persulfate and sodium p-styrene sulfonate into a heated mixed solution of sodium carboxymethylcellulose and water, reacting, then adding sodium hydrogen persulfate and methallyl polyoxyethylene ether, and reacting to obtain a modified sodium carboxymethylcellulose polymer solution;

(2) adding stearic acid into heated water, stirring, adding carbon, stirring, finally adding sodium hydroxide, cooling, adding calcium carbonate, cooling after complete reaction, adding ammonia water, and stirring to obtain a milky viscous liquid;

(3) mixing starch ether, stearic acid, polyvinyl alcohol, sodium dodecyl benzene sulfonate and maleimide aqueous solution to obtain a mixed solution;

(4) and (3) mixing the mixed solution obtained in the step (3) with water, heating, dropwise adding the modified sodium carboxymethyl cellulose polymer solution obtained in the step (1) on one side, dropwise adding the milky viscous liquid obtained in the step (2) on the other side, dropwise adding a calcium formate aqueous solution after the addition is finished, and neutralizing with sodium hydroxide after reaction to obtain the underwater anti-dispersant for the underwater grouting slurry material.

In a preferred embodiment of the present invention, the modified sodium carboxymethyl cellulose polymer solution prepared in step (1) comprises the following raw materials: adding 0.05-0.15 part of sodium hydrogen persulfate and 0.5-2 parts of sodium p-styrene sulfonate into a heated mixed solution of 3-5 parts of sodium carboxymethylcellulose and 25-35 parts of water, reacting, then adding 0.05-0.15 part of sodium hydrogen persulfate and 0.05-0.15 part of methyl allyl polyoxyethylene ether, and reacting to obtain a modified sodium carboxymethylcellulose polymer solution with the mass fraction of 25-35%.

In a preferred embodiment of the invention, the heating temperature in the mixed solution of the heated sodium carboxymethyl cellulose and the water in the step (1) is 60-80 ℃; adding sodium hydrogen persulfate and sodium p-styrene sulfonate, and reacting for 25-40 min; adding the methyl allyl polyoxyethylene ether, and then keeping the temperature for reaction for 0.5-1.5 hours.

In a preferred embodiment of the present invention, the methallyl polyoxyethylene ether in step (1) is added dropwise over a period of 25 to 40 minutes.

In a preferred embodiment of the present invention, the content of the raw materials of the milky viscous liquid prepared in step (2) is as follows: adding 1-3 parts of stearic acid into 250 parts of heated 150-one water, stirring, adding 2-4 parts of carbon, stirring, finally adding 5-8 parts of sodium hydroxide, cooling, adding 6-8 parts of calcium carbonate, cooling after complete reaction, adding 28-32 parts of ammonia water, and stirring to obtain a milky viscous liquid.

In a preferred embodiment of the present invention, the temperature of the water in step (2) is 45-55 ℃; adding sodium hydroxide, and cooling to 28-33 deg.C; the temperature to which the calcium carbonate is cooled after addition is 18-22 ℃.

In a preferred embodiment of the invention, stearic acid is added in the step (2) and stirred for 0.5-2 minutes; adding carbon and stirring for 0.3-1 min; adding ammonia water and stirring for 1-3 min.

In a preferred embodiment of the present invention, the mixed solution in step (3) comprises the following components: 1-3 parts of starch ether, 5-7 parts of stearic acid, 2-4 parts of polyvinyl alcohol, 5-7 parts of sodium dodecyl benzene sulfonate and 9-11 parts of maleimide aqueous solution by mass; the mass fraction of the maleimide aqueous solution is 4-6% of maleimide aqueous solution.

In a preferred embodiment of the present invention, the specific steps in step (4) are: and (3) mixing and heating 20 parts of mixed solution obtained in the step (3) with 18-23 parts of water, dropwise adding 5-8 parts of modified sodium carboxymethyl cellulose polymer solution obtained in the step (1) on one side, dropwise adding 5-8 parts of milky viscous liquid obtained in the step (2) on the other side, finally dropwise adding 6-10 parts of calcium formate aqueous solution after the addition is finished, and neutralizing with sodium hydroxide after reaction to obtain the underwater anti-dispersing agent for the underwater grouting slurry material.

In a preferred embodiment of the present invention, the mixture in step (4) is mixed with water and then heated to 75-85 ℃; the dropping time of the modified sodium carboxymethyl cellulose polymer solution and the milky viscous liquid is 4.5 to 6 hours; the calcium formate aqueous solution is 9-11% by mass; the dropping time of the calcium formate aqueous solution is 80-100min, and the temperature is kept for 2-3 hours after the dropping is finished; the pH was neutralized to 7 with sodium hydroxide.

The invention has the beneficial effects that: the underwater anti-dispersant prepared by the preparation method for the underwater grouting material has excellent performance and strong function, can ensure that the cement-based grouting material has good rheological property, has no dispersion in water during underwater grouting construction, has strong current scouring resistance and has no obvious loss of strength after water is condensed.

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.

The first embodiment is as follows:

the preparation method of the underwater anti-dispersing agent for the underwater grouting material comprises the following steps:

(1) adding 4 parts by mass of sodium carboxymethylcellulose and 30 parts by mass of distilled water into a three-necked flask provided with a thermometer, a stirrer, a reflux condensing device, a dropping funnel and a nitrogen protection device, and heating to 70 ℃; simultaneously adding 0.1 part of sodium hydrogen persulfate and 1 part of sodium p-styrene sulfonate; after reacting for 30min, adding 0.1 part of sodium hydrogen persulfate, dropwise adding 1 part of methyl allyl polyoxyethylene ether by using a constant-pressure low-liquid funnel, after the dropwise adding is finished for 30min, preserving the temperature for 1h, and closing a stirrer to obtain a modified sodium carboxymethylcellulose polymer solution with the mass fraction of 30%;

(2) 200 parts of water heated to 50 ℃ is filled in a three-mouth bottle provided with a thermometer, a stirrer, a reflux condensing device, a dropping funnel and a nitrogen protection device, 2 parts of stearic acid is added, 3 parts of carbon is added after stirring for 1 minute, 6 parts of sodium hydroxide is added after half minute, 7 parts of calcium carbonate is added when the temperature is reduced to 30 ℃, 30 parts of ammonia water is added after the reaction is completed and the temperature is cooled to 20 ℃, and the mixture is stirred for 2 minutes to form milky viscous liquid;

(3) weighing and mixing 2 parts of starch ether, 6 parts of stearic acid, 3 parts of polyvinyl alcohol, 6 parts of sodium dodecyl benzene sulfonate and 10 parts of maleimide aqueous solution with the mass fraction of 5% to obtain a mixed solution;

(4) and (2) mixing 20 parts of mixed solution obtained in the step (3) with 20 parts of water in a three-mouth bottle provided with a thermometer, a stirrer, a reflux condensing device, a dropping funnel and a nitrogen protection device, heating to 80 ℃, dropwise adding 6 parts of modified sodium carboxymethyl cellulose polymer solution obtained in the step (1) on one side, dropwise adding 6 parts of milky viscous liquid obtained in the step (2) on the other side, uniformly dropwise adding for 5 hours, dropwise adding 8 parts of calcium formate aqueous solution with the mass fraction of 10% after finishing dropping, keeping the temperature for 2.5 hours after 90 minutes, and finally neutralizing the pH value to 7 with sodium hydroxide to obtain the underwater anti-dispersing agent for underwater grouting slurry materials.

Example two:

the preparation method of the underwater anti-dispersing agent for the underwater grouting material comprises the following steps:

(1) adding 3 parts by mass of sodium carboxymethylcellulose and 25 parts by mass of distilled water into a three-necked flask provided with a thermometer, a stirrer, a reflux condensing device, a dropping funnel and a nitrogen protection device, and heating to 80 ℃; simultaneously adding 0.05 part of sodium hydrogen persulfate and 0.5 part of sodium p-styrene sulfonate; after reacting for 25min, adding 0.15 part of sodium hydrogen persulfate, dropwise adding 0.15 part of methyl allyl polyoxyethylene ether by using a constant-pressure low-liquid funnel, after finishing dropwise adding for 40min, preserving heat for 0.5h, and closing a stirrer to obtain a modified sodium carboxymethylcellulose polymer solution with the mass fraction of 25%;

(2) 150 parts of water heated to 45 ℃ is filled in a three-mouth bottle provided with a thermometer, a stirrer, a reflux condensing device, a dropping funnel and a nitrogen protection device, 1 part of stearic acid is added, 2 parts of carbon is added after stirring for 0.5 minute, 5 parts of sodium hydroxide is added after 0.3 minute, 6 parts of calcium carbonate is added when the temperature is reduced to 28 ℃, 28 parts of ammonia water is added after complete reaction is cooled to 18 ℃, and milky viscous liquid is obtained after stirring for 1 minute;

(3) weighing and mixing 1 part of starch ether, 5 parts of stearic acid, 2 parts of polyvinyl alcohol, 5 parts of sodium dodecyl benzene sulfonate and 9 parts of maleimide aqueous solution with the mass fraction of 5% to obtain a mixed solution;

(4) and (2) mixing 20 parts of mixed solution obtained in the step (3) with 18 parts of water in a three-mouth bottle provided with a thermometer, a stirrer, a reflux condensing device, a dropping funnel and a nitrogen protection device, heating to 80 ℃, dropwise adding 5 parts of modified sodium carboxymethyl cellulose polymer solution obtained in the step (1) on one side, dropwise adding 5 parts of milky viscous liquid obtained in the step (2) on the other side, uniformly dropwise adding for 5 hours, dropwise adding 6 parts of calcium formate aqueous solution with the mass fraction of 10% after finishing dropping, keeping the temperature for 2.5 hours after 90 minutes, and finally neutralizing the pH value to 7 with sodium hydroxide to obtain the underwater anti-dispersing agent for underwater grouting slurry materials.

Example three:

the preparation method of the underwater anti-dispersing agent for the underwater grouting material comprises the following steps:

(1) adding 5 parts by mass of sodium carboxymethylcellulose and 35 parts by mass of distilled water into a three-necked flask provided with a thermometer, a stirrer, a reflux condensing device, a dropping funnel and a nitrogen protection device, and heating to 60 ℃; simultaneously adding 0.15 part of sodium hydrogen persulfate and 2 parts of sodium p-styrene sulfonate; after reacting for 40min, adding 0.05 part of sodium hydrogen persulfate, dropwise adding 0.05 part of methyl allyl polyoxyethylene ether by using a constant-pressure low-liquid funnel, after the dropwise adding is finished for 25min, preserving the temperature for 1.5h, and closing the stirrer to obtain a modified sodium carboxymethylcellulose polymer solution with the mass fraction of 35%;

(2) 250 parts of water heated to 55 ℃ is filled in a three-mouth bottle provided with a thermometer, a stirrer, a reflux condensing device, a dropping funnel and a nitrogen protection device, 3 parts of stearic acid is added, 4 parts of carbon is added after stirring for 2 minutes, 8 parts of sodium hydroxide is added after 1 minute, 8 parts of calcium carbonate is added when the temperature is reduced to 33 ℃, 32 parts of ammonia water is added after the reaction is completed and the temperature is cooled to 22 ℃, and the mixture is stirred for 3 minutes to form milky viscous liquid;

(3) weighing and mixing 3 parts of starch ether, 7 parts of stearic acid, 4 parts of polyvinyl alcohol, 7 parts of sodium dodecyl benzene sulfonate and 11 parts of maleimide aqueous solution with the mass fraction of 5% to obtain a mixed solution;

(4) and (2) mixing 20 parts of mixed solution obtained in the step (3) with 23 parts of water in a three-mouth bottle provided with a thermometer, a stirrer, a reflux condensing device, a dropping funnel and a nitrogen protection device, heating to 80 ℃, dropwise adding 8 parts of modified sodium carboxymethyl cellulose polymer solution obtained in the step (1) on one side, dropwise adding 8 parts of milky viscous liquid obtained in the step (2) on the other side, uniformly dropwise adding for 5 hours, dropwise adding 10 parts of calcium formate aqueous solution with the mass fraction of 10% after finishing dropping, keeping the temperature for 2.5 hours after 90 minutes, and finally neutralizing the pH value to 7 with sodium hydroxide to obtain the underwater anti-dispersing agent for underwater grouting slurry materials.

The invention has the beneficial effects that:

the prepared underwater anti-dispersant has excellent performance and strong function, can keep good rheological property of a cement-based material, is not dispersed when entering water during underwater pouring construction, and has strong water flow scouring resistance;

secondly, the strength of the prepared underwater anti-dispersing agent is not obviously lost after the underwater anti-dispersing agent is condensed in water, the pH value of the water is not over standard, the content of suspended solids is low, and the parameters such as the pH value of the water, the content of the suspended solids, the condensing time and the like reach the first-class specified indexes in GB/T37990-;

thirdly, the prepared underwater anti-dispersing agent contains a chemically modified high molecular polymer, and methoxy and hydroxypropyl groups on the molecular chain of the polymer are combined with calcium ions and aluminum ions in cement molecules to form viscous gel, so that cement-based material slurry is more compact and has strong anti-dispersion property;

fourthly, the prepared underwater anti-dispersant contains modified organic polymer hydrophobic groups (hydrocarbon group CnH)_2n+1) The surface of the cement-based material can generate certain hydrophobicity, and the water-entering dispersibility resistance and water flow scouring resistance of the material are enhanced.

The above description is only an embodiment of the present invention, and not intended to limit the scope of the present invention, and all modifications of equivalent structures and equivalent processes, which are made by the present specification, or directly or indirectly applied to other related technical fields, are included in the scope of the present invention.