阅读说明：本技术 一种超级早强聚羧酸减水剂及其制备方法 (Super early-strength polycarboxylate superplasticizer and preparation method thereof ) 是由 邵源 许代鹏 陈龙华 于 2020-12-23 设计创作，主要内容包括：本发明属于本发明涉及减水剂及其制备技术领域,提供了一种超级早强聚羧酸减水剂及其制备方法,该超级早强聚羧酸减水剂由异戊烯醇聚氧乙烯醚、超早强功能单体酯、丙烯酸、丙烯酰胺、链转移剂、双氧水溶液、抗坏血酸、氢氧化钠溶液混合制备而成,本发明配方体系中引入超早强功能单体酯能够提高混凝土的早期强度,因为聚羧酸减水剂中的早强基团在水泥体系中,能够通过的氢键吸附大量的水,形成吸附水化膜,有效防止水泥颗粒的凝聚,增加水泥浆中细颗粒的含量,有效地降低失水量,使得混凝土强度得到显著提高。(The invention belongs to the technical field of water reducing agents and preparation thereof, and provides a super early strength polycarboxylate water reducing agent and a preparation method thereof.)

1. A super early strength polycarboxylate superplasticizer is characterized in that: the super early strength polycarboxylate water reducer is prepared by mixing 80-120 parts by weight of isoamylol polyoxyethylene ether, 1-8 parts by weight of super early strength functional monomer ester, 30-60 parts by weight of acrylic acid, 1-8 parts by weight of acrylamide, 2-5 parts by weight of chain transfer agent, 1-5 parts by weight of hydrogen peroxide solution, 0.5-2 parts by weight of ascorbic acid and 1-5 parts by weight of sodium hydroxide solution;

the preparation method of the super early strength functional monomer ester comprises the following steps: adding methanol and tartaric acid into a reaction kettle, heating to 20-40 ℃, adding maleic anhydride, heating to 50-70 ℃ after dissolution, adding a catalyst and triethanolamine after sealing reaction for 1-3h, heating to 100-130 ℃, and reacting for 2-4h to obtain the ultra-early-strength functional monomer ester.

2. The super early strength polycarboxylate superplasticizer according to claim 1, characterized in that: the molecular weight of the prenol polyoxyethylene ether is at least one of 2400 and 5000.

3. The super early strength polycarboxylate superplasticizer according to claim 1, characterized in that: the chain transfer agent is at least one of sodium methallyl sulfonate, sodium allyl sulfonate, sodium bisulfite, thioglycolic acid and mercaptopropionic acid.

4. The super early strength polycarboxylate superplasticizer according to claim 2, characterized in that: the mass ratio of the isoamylol polyoxyethylene ether with the molecular weight of 2400 to the isoamylol polyoxyethylene ether with the molecular weight of 5000 is (0.25-1.75): 1.

5. The super early strength polycarboxylate superplasticizer according to claim 1, characterized in that: amount of the methanol substance: amount of tartaric acid species: amount of maleic anhydride substance: amount of catalyst material: the amount of triethanolamine substance is 1: (0.95-1.05): (0.95-1.05): (1-2): (0.95-1.05).

6. The super early strength polycarboxylate superplasticizer according to any one of claims 1 or 5, characterized in that: the catalyst is at least one of alkali metal, alkali metal hydroxide, alkaline earth metal hydroxide and alkali metal oxide.

7. The super early strength polycarboxylate superplasticizer according to claim 1, characterized in that: the concentration of the hydrogen peroxide solution is 25-30%.

8. The super early strength polycarboxylate superplasticizer according to claim 1, characterized in that: the concentration of the sodium hydroxide solution is 30-40 wt%.

9. A preparation method of a super early strength polycarboxylate superplasticizer is characterized by comprising the following steps: the preparation method of the super early-strength polycarboxylate superplasticizer comprises the following steps:

the method comprises the following steps: adding water and prenol polyoxyethylene ether into a reaction kettle, and stirring for 8-12min to obtain a prenol polyoxyethylene ether solution;

step two: adding hydrogen peroxide solution, chain transfer agent and super early strength functional monomer ester into the prenyl alcohol polyoxyethylene ether solution obtained in the step one, and uniformly stirring for 4-6min to obtain a mixture A;

step three: preparing an acrylic acid solution and a mixed solution of acrylamide and ascorbic acid, simultaneously adding the acrylic acid solution and the mixed solution of acrylamide and ascorbic acid into the mixture A in the second step, wherein the dripping time of the acrylic acid solution and the mixed solution of acrylamide and ascorbic acid is 2-3h, and after the dripping is finished, preserving heat for 1-2h to obtain a mixture B;

step four: and adding a sodium hydroxide solution into the mixture B obtained in the third step to neutralize the pH value to 6-8, and uniformly stirring to obtain the super early-strength polycarboxylate superplasticizer.

Technical Field

The invention relates to the technical field of water reducing agents and preparation thereof, and particularly relates to a super early-strength polycarboxylate water reducing agent and a preparation method thereof.

Background

The polycarboxylic acid high-performance water reducing agent has the advantages of environmental protection, low mixing amount, high water reducing rate, good slump retaining performance and the like, so the polycarboxylic acid high-performance water reducing agent is widely applied to various construction projects, but with continuous popularization and application of polycarboxylic acid water reducing series products, the concrete technology is continuously improved, and the polycarboxylic acid high-performance water reducing agent is found to have certain defects in special environments, such as slow early strength rise, direct influence on concrete mold dismantling and limitation on application of the polycarboxylic acid water reducing agent in certain constructional projects. Therefore, the early-strength polycarboxylate superplasticizer has great significance for researching precast concrete, improving the early strength and shortening the service cycle of a concrete template.

Disclosure of Invention

In order to solve the problems, the invention provides a super early strength polycarboxylate superplasticizer and a preparation method thereof, wherein the super early strength polycarboxylate superplasticizer has the characteristic of super early strength, and can improve the flow rate, the water reducing rate and the slump retaining performance of concrete, and the concrete content of the super early strength polycarboxylate superplasticizer is as follows:

the invention aims to provide a super early strength polycarboxylate superplasticizer, which is characterized by comprising the following technical points: the super early strength polycarboxylate water reducer is prepared by mixing 80-120 parts by weight of isoamylol polyoxyethylene ether, 1-8 parts by weight of super early strength functional monomer ester, 30-60 parts by weight of acrylic acid, 1-8 parts by weight of acrylamide, 2-5 parts by weight of chain transfer agent, 1-5 parts by weight of hydrogen peroxide solution, 0.5-2 parts by weight of ascorbic acid and 1-5 parts by weight of sodium hydroxide solution;

the preparation method of the monomer ester with the super early strength function in the formula system comprises the following steps: adding methanol and tartaric acid into a reaction kettle, heating to 20-40 ℃, adding maleic anhydride, heating to 50-70 ℃ after dissolution, adding a catalyst and triethanolamine after sealing reaction for 1-3h, heating to 100-130 ℃, and reacting for 2-4h to obtain the ultra-early-strength functional monomer ester.

In some embodiments of the present invention, the molecular weight of the prenyl polyoxyethylene ether in the formulation of the super early strength polycarboxylate water reducer of the present invention is at least one of 2400 and 5000.

In some embodiments of the present invention, the chain transfer agent in the formula system of the super early strength polycarboxylate water reducer of the present invention is at least one of sodium methallyl sulfonate, sodium allyl sulfonate, sodium bisulfite, thioglycolic acid and mercaptopropionic acid.

In some embodiments of the invention, the amount ratio of the prenyl alcohol polyoxyethylene ether with the molecular weight of 2400 to the prenyl alcohol polyoxyethylene ether with the molecular weight of 5000 used in the formula system of the super early-strength polycarboxylate superplasticizer of the invention is (0.25-1.75): 1.

In some embodiments of the present invention, the amount of methanol in the formulation system of the super early strength polycarboxylate water reducer of the present invention is: amount of tartaric acid species: amount of maleic anhydride substance: amount of catalyst material: the amount of triethanolamine substance is 1: (0.95-1.05): (0.95-1.05): (1-2): (0.95-1.05).

In some embodiments of the present invention, the catalyst in the formulation system of the super early strength polycarboxylate water reducer of the present invention is at least one of alkali metal, alkali metal hydroxide, alkaline earth metal hydroxide and alkali metal oxide.

In some embodiments of the present invention, the concentration of the hydrogen peroxide solution in the formula system of the super early-strength polycarboxylate superplasticizer of the present invention is 25-30%.

In some embodiments of the present invention, the concentration of the sodium hydroxide solution in the formulation system of the super early strength polycarboxylate superplasticizer of the present invention is 30-40 wt%.

The second purpose of the invention is to provide a preparation method of the super early strength polycarboxylate superplasticizer, which has the technical points that: the preparation method of the super early-strength polycarboxylate superplasticizer comprises the following steps:

the method comprises the following steps: adding water and prenol polyoxyethylene ether into a reaction kettle, and stirring for 8-12min to obtain a prenol polyoxyethylene ether solution;

step two: adding hydrogen peroxide solution, chain transfer agent and super early strength functional monomer ester into the prenyl alcohol polyoxyethylene ether solution obtained in the step one, and uniformly stirring for 4-6min to obtain a mixture A;

step three: preparing an acrylic acid solution and a mixed solution of acrylamide and ascorbic acid, simultaneously adding the acrylic acid solution and the mixed solution of acrylamide and ascorbic acid into the mixture A in the second step, wherein the dripping time of the acrylic acid solution and the mixed solution of acrylamide and ascorbic acid is 2-3h, and after the dripping is finished, preserving heat for 1-2h to obtain a mixture B;

step four: and adding a sodium hydroxide solution into the mixture B obtained in the third step to neutralize the pH value to 6-8, and uniformly stirring to obtain the super early-strength polycarboxylate superplasticizer.

Compared with the prior art, the invention has the beneficial effects that:

the super early strength polycarboxylate water reducer is prepared by mixing isopentenol polyoxyethylene ether, super early strength functional monomer ester, acrylic acid, acrylamide, a chain transfer agent, a hydrogen peroxide solution, ascorbic acid and a sodium hydroxide solution.

Detailed Description

The technical solutions in the embodiments of the present invention will be clearly and completely described below so that those skilled in the art can better understand the advantages and features of the present invention, and thus the scope of the present invention will be more clearly defined. The embodiments described herein are only a few embodiments of the present invention, rather than all embodiments, and all other embodiments that can be derived by one of ordinary skill in the art without inventive faculty based on the embodiments described herein are intended to fall within the scope of the present invention.

Example 1

The super early strength polycarboxylate water reducer is prepared by mixing 100kg of isoamylene alcohol polyoxyethylene ether, 4.5kg of super early strength functional monomer ester, 45kg of acrylic acid, 4.5kg of acrylamide, 3.5kg of chain transfer agent, 3kg of hydrogen peroxide solution, 1.25kg of ascorbic acid and 3kg of sodium hydroxide solution;

the preparation method of the monomer ester with the super early strength function in the formula system comprises the following steps: adding methanol and tartaric acid into a reaction kettle, heating to 30 ℃, adding maleic anhydride, dissolving, heating to 60 ℃, sealing for reaction for 2 hours, adding a catalyst and triethanolamine, heating to 115 ℃, and reacting for 3 hours to obtain the ultra-early-strength functional monomer ester.

Wherein, the molecular weight of the prenyl alcohol polyoxyethylene ether in the formula system of the super early strength polycarboxylate superplasticizer is 2400-5000 mixture.

The chain transfer agent in the formula system of the super early strength polycarboxylate superplasticizer is sodium methyl propylene sulfonate.

The weight ratio of the isoamylol polyoxyethylene ether with the molecular weight of 2400 to the isoamylol polyoxyethylene ether with the molecular weight of 5000 used in the formula system of the super early-strength polycarboxylate superplasticizer is 1: 1.

The amount of methanol substances in the formula system of the super early strength polycarboxylate superplasticizer is as follows: amount of tartaric acid species: amount of maleic anhydride substance: amount of catalyst material: the amount of triethanolamine substance is 1: 1: 1: 1.5: 1.

the catalyst in the formula system of the super early strength polycarboxylate superplasticizer is alkali metal.

Wherein, the concentration of the hydrogen peroxide solution in the formula system of the super early strength polycarboxylate superplasticizer is 27.5%.

Wherein, the concentration of the sodium hydroxide solution in the formula system of the super early strength polycarboxylate superplasticizer is 35 wt%.

According to the formula, the preparation method of the super early strength polycarboxylate superplasticizer comprises the following steps:

the method comprises the following steps: adding water and prenol polyoxyethylene ether into a reaction kettle, and stirring for 10min to obtain a prenol polyoxyethylene ether solution;

step two: adding hydrogen peroxide solution, chain transfer agent and super early strength functional monomer ester into the prenyl alcohol polyoxyethylene ether solution obtained in the step one, and uniformly stirring for 5min to obtain a mixture A;

step three: preparing an acrylic acid solution and a mixed solution of acrylamide and ascorbic acid, simultaneously adding the acrylic acid solution and the mixed solution of acrylamide and ascorbic acid into the mixture A in the second step, wherein the dripping time of the acrylic acid solution and the mixed solution of acrylamide and ascorbic acid is 2.5h, and after the dripping is finished, keeping the temperature for 1.5h to obtain a mixture B;

step four: and thirdly, adding a sodium hydroxide solution into the mixture B obtained in the third step to neutralize the pH value to 7, and uniformly stirring to obtain the super early-strength polycarboxylate superplasticizer.

Example 2

A super early strength polycarboxylate water reducer is prepared by mixing 80kg of isoamylol polyoxyethylene ether, 1kg of super early strength functional monomer ester, 30kg of acrylic acid, 1kg of acrylamide, 2kg of chain transfer agent, 1kg of hydrogen peroxide solution, 0.5kg of ascorbic acid and 1kg of sodium hydroxide solution;

the preparation method of the monomer ester with the super early strength function in the formula system comprises the following steps: adding methanol and tartaric acid into a reaction kettle, heating to 20 ℃, adding maleic anhydride, dissolving, heating to 50 ℃, sealing for reaction for 1h, adding a catalyst and triethanolamine, heating to 100 ℃, and reacting for 2h to obtain the ultra-early-strength functional monomer ester.

Wherein, the molecular weight of the prenyl alcohol polyoxyethylene ether in the formula system of the super early strength polycarboxylate superplasticizer is 2400-5000 mixture.

The chain transfer agent in the formula system of the super early strength polycarboxylate superplasticizer is sodium allylsulfonate.

The weight ratio of the isoamylol polyoxyethylene ether with the molecular weight of 2400 to the isoamylol polyoxyethylene ether with the molecular weight of 5000 used in the formula system of the super early-strength polycarboxylate superplasticizer is 0.25: 1.

The amount of methanol substances in the formula system of the super early strength polycarboxylate superplasticizer is as follows: amount of tartaric acid species: amount of maleic anhydride substance: amount of catalyst material: the amount of triethanolamine substance is 1: 0.95: 0.95: 1: 0.95.

the catalyst in the formula system of the super early strength polycarboxylate superplasticizer is alkali metal hydroxide.

Wherein, the concentration of the hydrogen peroxide solution in the formula system of the super early strength polycarboxylate superplasticizer is 25%.

Wherein, the concentration of the sodium hydroxide solution in the formula system of the super early strength polycarboxylate superplasticizer is 30 wt%.

According to the formula, the preparation method of the super early strength polycarboxylate superplasticizer comprises the following steps:

the method comprises the following steps: adding water and prenol polyoxyethylene ether into a reaction kettle, and stirring for 8min to obtain a prenol polyoxyethylene ether solution;

step two: adding hydrogen peroxide solution, chain transfer agent and super early strength functional monomer ester into the prenyl alcohol polyoxyethylene ether solution obtained in the step one, and uniformly stirring for 4min to obtain a mixture A;

step three: preparing an acrylic acid solution and a mixed solution of acrylamide and ascorbic acid, simultaneously adding the acrylic acid solution and the mixed solution of acrylamide and ascorbic acid into the mixture A in the second step, wherein the dripping time of the acrylic acid solution and the mixed solution of acrylamide and ascorbic acid is 2 hours, and after the dripping is finished, keeping the temperature for 1 hour to obtain a mixture B;

step four: and adding a sodium hydroxide solution into the mixture B obtained in the third step to neutralize the pH value to 6, and uniformly stirring to obtain the super early-strength polycarboxylate superplasticizer.

Example 3

A super early strength polycarboxylate water reducer is prepared by mixing 120kg of isoamylol polyoxyethylene ether, 8kg of super early strength functional monomer ester, 60kg of acrylic acid, 8kg of acrylamide, 5kg of chain transfer agent, 5kg of hydrogen peroxide solution, 2kg of ascorbic acid and 5kg of sodium hydroxide solution;

the preparation method of the monomer ester with the super early strength function in the formula system comprises the following steps: adding methanol and tartaric acid into a reaction kettle, heating to 40 ℃, adding maleic anhydride, dissolving, heating to 70 ℃, sealing, reacting for 3 hours, adding a catalyst and triethanolamine, heating to 130 ℃, and reacting for 4 hours to obtain the ultra-early-strength functional monomer ester.

Wherein, the molecular weight of the prenyl alcohol polyoxyethylene ether in the formula system of the super early strength polycarboxylate superplasticizer is 2400-5000 mixture.

The chain transfer agent in the formula system of the super early strength polycarboxylate superplasticizer is sodium bisulfite.

The weight ratio of the isoamylol polyoxyethylene ether with the molecular weight of 2400 to the isoamylol polyoxyethylene ether with the molecular weight of 5000 in the formula system of the super early-strength polycarboxylate superplasticizer is 1.75: 1.

The amount of methanol substances in the formula system of the super early strength polycarboxylate superplasticizer is as follows: amount of tartaric acid species: amount of maleic anhydride substance: amount of catalyst material: the amount of triethanolamine substance is 1: 1.05: 1.05: 2: 1.05.

the catalyst in the formula system of the super early strength polycarboxylate superplasticizer is alkaline earth metal hydroxide.

Wherein, the concentration of the hydrogen peroxide solution in the formula system of the super early strength polycarboxylate superplasticizer is 30%.

Wherein, the concentration of the sodium hydroxide solution in the formula system of the super early strength polycarboxylate superplasticizer is 40 wt%.

According to the formula, the preparation method of the super early strength polycarboxylate superplasticizer comprises the following steps:

the method comprises the following steps: adding water and prenol polyoxyethylene ether into a reaction kettle, and stirring for 12min to obtain a prenol polyoxyethylene ether solution;

step two: adding hydrogen peroxide solution, chain transfer agent and super early strength functional monomer ester into the prenyl alcohol polyoxyethylene ether solution obtained in the step one, and uniformly stirring for 6min to obtain a mixture A;

step three: preparing an acrylic acid solution and a mixed solution of acrylamide and ascorbic acid, simultaneously adding the acrylic acid solution and the mixed solution of acrylamide and ascorbic acid into the mixture A in the second step, wherein the dripping time of the acrylic acid solution and the mixed solution of acrylamide and ascorbic acid is 3 hours, and preserving heat for 2 hours after the dripping is finished to obtain a mixture B;

step four: and thirdly, adding a sodium hydroxide solution into the mixture B obtained in the third step to neutralize the pH value to 8, and uniformly stirring to obtain the super early-strength polycarboxylate superplasticizer.

Example 4

A super early strength polycarboxylate water reducer is prepared by mixing 90kg of isoamylol polyoxyethylene ether, 2kg of super early strength functional monomer ester, 40kg of acrylic acid, 2kg of acrylamide, 3kg of chain transfer agent, 2kg of hydrogen peroxide solution, 0.8kg of ascorbic acid and 2kg of sodium hydroxide solution;

the preparation method of the monomer ester with the super early strength function in the formula system comprises the following steps: adding methanol and tartaric acid into a reaction kettle, heating to 25 ℃, adding maleic anhydride, dissolving, heating to 55 ℃, sealing for reaction for 2 hours, adding a catalyst and triethanolamine, heating to 110 ℃, and reacting for 3 hours to obtain the ultra-early-strength functional monomer ester.

Wherein, the molecular weight of the prenyl alcohol polyoxyethylene ether in the formula system of the super early strength polycarboxylate superplasticizer is 2400-5000 mixture.

The chain transfer agent in the formula system of the super early strength polycarboxylate superplasticizer is thioglycolic acid.

The weight ratio of the isoamylol polyoxyethylene ether with the molecular weight of 2400 to the isoamylol polyoxyethylene ether with the molecular weight of 5000 in the formula system of the super early-strength polycarboxylate superplasticizer is 1.5: 1.

The amount of methanol substances in the formula system of the super early strength polycarboxylate superplasticizer is as follows: amount of tartaric acid species: amount of maleic anhydride substance: amount of catalyst material: the amount of triethanolamine substance is 1: 1: 1: 1.2: 1.

the catalyst in the formula system of the super early strength polycarboxylate superplasticizer is at least one of alkali metal, alkali metal hydroxide, alkaline earth metal hydroxide and alkali metal oxide.

Wherein, the concentration of the hydrogen peroxide solution in the formula system of the super early strength polycarboxylate superplasticizer is 26%.

Wherein, the concentration of the sodium hydroxide solution in the formula system of the super early strength polycarboxylate superplasticizer is 32 wt%.

According to the formula, the preparation method of the super early strength polycarboxylate superplasticizer comprises the following steps:

the method comprises the following steps: adding water and isoamylol polyoxyethylene ether into a reaction kettle, and stirring for 9min to obtain an isoamylol polyoxyethylene ether solution;

step two: adding hydrogen peroxide solution, chain transfer agent and super early strength functional monomer ester into the prenyl alcohol polyoxyethylene ether solution obtained in the step one, and uniformly stirring for 4.5min to obtain a mixture A;

step three: preparing an acrylic acid solution and a mixed solution of acrylamide and ascorbic acid, simultaneously adding the acrylic acid solution and the mixed solution of acrylamide and ascorbic acid into the mixture A in the second step, wherein the dripping time of the acrylic acid solution and the mixed solution of acrylamide and ascorbic acid is 2 hours, and after the dripping is finished, keeping the temperature for 1 hour to obtain a mixture B;

step four: and adding a sodium hydroxide solution into the mixture B obtained in the third step to neutralize the pH value to 6.2, and uniformly stirring to obtain the super early-strength polycarboxylate superplasticizer.

Examples of the experiments

The super early strength polycarboxylate superplasticizers prepared in the embodiments 1 to 4 are subjected to performance tests according to the enterprise standard Q/320800HMS1-2017, and the specific test data are shown in Table 1:

TABLE 1

Finally, it should be noted that the above embodiments are only used for illustrating the technical solutions of the present invention, and not for limiting the protection scope of the present invention, although the present invention is described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that modifications or equivalent substitutions can be made on the technical solutions of the present invention without departing from the spirit and scope of the technical solutions of the present invention.