阅读说明：本技术 一种混凝土添加剂及其制备方法 (Concrete additive and preparation method thereof ) 是由 韩昌龙 于 2020-08-12 设计创作，主要内容包括：本发明公开了一种混凝土添加剂,其特征在于,包括按重量份计的下列组分：磷酸基均三嗪基超支化大分子化合物2-5份、磺酸基二乙醇胺/1,3-金刚烷二乙酸缩聚物8-12份、凹凸棒土1-3份、氧化石墨烯纤维1-4份。本发明还公开了所述混凝土添加剂的制备方法。本发明公开的混凝土添加剂减水效果更优异,掺量更少,环保性和增塑效果更佳,功能多样,提高和改善混凝土材料强度、流动性、耐久性和抗渗性能效果更显著,对混凝土综合性能没有负面影响,具有较高的经济价值、社会价值和生态价值。(The invention discloses a concrete additive which is characterized by comprising the following components in parts by weight: 2-5 parts of phosphate s-triazine hyperbranched macromolecular compound, 8-12 parts of sulfonic diethanolamine/1, 3-adamantane diacetic acid polycondensate, 1-3 parts of attapulgite and 1-4 parts of graphene oxide fiber. The invention also discloses a preparation method of the concrete additive. The concrete additive disclosed by the invention has the advantages of more excellent water reducing effect, less mixing amount, better environmental protection and plasticizing effect, multiple functions, more obvious effects of improving the strength, the fluidity, the durability and the impermeability of a concrete material, no negative influence on the comprehensive performance of the concrete, and higher economic value, social value and ecological value.)

1. The concrete additive is characterized by comprising the following components in parts by weight: 2-5 parts of phosphate s-triazine hyperbranched macromolecular compound, 8-12 parts of sulfonic diethanolamine/1, 3-adamantane diacetic acid polycondensate, 1-3 parts of attapulgite and 1-4 parts of graphene oxide fiber.

2. The concrete additive according to claim 1, wherein the preparation method of the phosphate-s-triazine hyperbranched macromolecular compound comprises the following steps: adding the s-triazine hyperbranched compound into an organic solvent, then adding chloromethyl phosphoric acid into the organic solvent, stirring and reacting for 4-6 hours at the temperature of 40-60 ℃, then performing rotary evaporation to remove the solvent, washing the crude product for 3-5 times by using diethyl ether, and then performing rotary evaporation to remove the diethyl ether to obtain the phosphate-s-triazine hyperbranched macromolecular compound.

3. The concrete additive as claimed in claim 2, wherein the mass ratio of the s-triazinyl hyperbranched compound, the organic solvent and the chloromethyl phosphoric acid is (3-4): (10-15): 1.

4. The concrete additive according to claim 2, wherein the organic solvent is any one of tetrahydrofuran, N-dimethylformamide, N-dimethylacetamide and N-methylpyrrolidone.

5. The concrete additive as claimed in claim 1, wherein the preparation method of the sulfonic diethanolamine/1, 3-adamantane diacetic acid polycondensate comprises the following steps:

step C1, adding diethanolamine, 1, 3-adamantane diacetic acid, dicyclohexyl carbodiimide and 4-dimethylamino pyridine into N-methylpyrrolidone, stirring and reacting for 6-8 hours at 30-50 ℃, then precipitating in water, washing the precipitated polymer with ethanol for 3-7 times, and finally drying in a vacuum drying oven at 80-90 ℃ to constant weight to obtain a diethanolamine/1, 3-adamantane diacetic acid polycondensate;

and step C2, adding the diethanolamine/1, 3-adamantane diacetic acid polycondensate prepared in the step C1 into an ethanol solution of 1, 4-butanesultone, stirring and reacting for 15-20 hours at 50-60 ℃ in the atmosphere of nitrogen or inert gas, then performing rotary evaporation to remove ethanol, washing the product with water for 3-6 times, and finally drying in a vacuum drying oven at 80-90 ℃ to constant weight to obtain the sulfonic diethanolamine/1, 3-adamantane diacetic acid polycondensate.

6. The concrete additive as claimed in claim 5, wherein the molar ratio of diethanolamine, 1, 3-adamantanediacetic acid, dicyclohexylcarbodiimide, 4-dimethylaminopyridine and N-methylpyrrolidone in step C1 is 1:1 (0.4-0.8) to 0.5 (8-14).

7. The concrete additive as claimed in claim 5, wherein the mass ratio of the diethanolamine/1, 3-adamantane diacetic acid polycondensate to the ethanol solution of 1, 4-butanesultone in the step C2 is 1 (5-10); the mass percentage concentration of the ethanol solution of the 1, 4-butanesultone is 15-25%.

8. The concrete additive according to claim 5, wherein the inert gas is any one of helium, neon and argon.

9. The concrete additive as claimed in claim 1, wherein the particle size of the attapulgite is 300-500 mesh; the length range of the graphene oxide fiber is 3-8 mm, and the diameter of the graphene oxide fiber is 100-400 nm.

10. A concrete additive according to any one of claims 1 to 9 wherein the method of preparation of the concrete additive comprises the steps of: the components are uniformly mixed according to a ratio to obtain a mixture, then the mixture is uniformly mixed with water with the mass being 3-5 times of the mass of the mixture, sodium hydroxide is added into the mixture, the PH value is adjusted to 7, then the mixture is dried, and the mixture is added into a ball mill for grinding for 15-25 minutes and then discharged.

Technical Field

The invention relates to the technical field of building materials, in particular to a concrete additive and a preparation method thereof.

Background

In recent years, with the progress of society and the development of economy, various buildings and construction projects, such as bamboo shoots in the spring after rain, are developed, and are crystals developed in times, a symbol of a city, which records the history and transition of the city, and are a mark of modern civilization. The use of construction materials is not left behind the buildings and construction projects representing modern cities, and the construction materials are necessary conditions for ensuring the quality of the construction projects and the safety of the buildings. The concrete is used as an indispensable building engineering material in the construction process of modern building engineering, and plays a vital role in ensuring the safety and quality of buildings.

Concrete, referred to as "concrete" for short, is usually prepared by mixing cement as a cementing material, sand and stone as aggregates, a concrete additive and water in a certain proportion, and stirring. Among them, the concrete additive is an important component of concrete, and is one of indispensable components for ensuring excellent workability, strength and durability of concrete, and the addition of such components can effectively improve and adjust the performance of concrete. However, the concrete additives in the prior art have single function, and a large amount of additives with different weights are required to be added simultaneously to obtain concrete with excellent comprehensive performance, but the addition of a large amount of additives can cause negative effects on the setting time and early and late strength of the concrete to different degrees due to the problem of caking property. Antagonism is easily generated among different additives. In addition, the concrete additives on the market have the defects of poor water reducing effect, large mixing amount, poor plasticizing effect, easy deterioration and poor concrete protection effect.

The Chinese patent with application number 201510631561.6 discloses a concrete additive, which comprises the following components in parts by weight: high-efficiency water reducing agent: 15-60wt%, organosilicon waterproofing agent: 1.0-5.0wt%, sodium beta-sulphonate formaldehyde condensate: 0.5-2.0wt%, triethanolamine: 1.5-3.5wt%, alkyl benzene sulfonate: 3.5-7.5%, sodium sulfate: 3.5-25wt%, silicone: 3.0-5.0wt% and the balance water. The additive has the effects of water seepage prevention and impact resistance, and obviously improves the strength and the friction resistance of concrete. However, the use of the component of the beta-sodium sulfonate formaldehyde condensate in the invention leads to poor environmental protection performance and is not beneficial to the realization of ecological value.

Therefore, the development of the concrete additive which has more excellent water reducing effect, less mixing amount, better environmental protection and plasticizing effect, various functions, more obvious effect of improving the strength, the fluidity, the durability and the impermeability of the concrete material, no negative influence on the comprehensive performance of the concrete meets the market demand, has wide market value and application prospect and has very important significance for promoting the development of the concrete industry.

Disclosure of Invention

The invention aims to overcome the defects of the prior art and provides a concrete additive and a preparation method thereof, wherein the preparation method is simple and easy to implement, convenient to operate and control, high in preparation efficiency and finished product qualification rate, small in equipment dependence and suitable for continuous large-scale production; the concrete additive prepared by the preparation method has the advantages of more excellent water reducing effect, less mixing amount, better environmental protection and plasticizing effect, various functions, more obvious effects of improving the strength, the fluidity, the durability and the impermeability of the concrete material, no negative influence on the comprehensive performance of the concrete, and higher economic value, social value and ecological value.

In order to achieve the purpose, the invention adopts the technical scheme that: the concrete additive is characterized by comprising the following components in parts by weight: 2-5 parts of phosphate s-triazine hyperbranched macromolecular compound, 8-12 parts of sulfonic diethanolamine/1, 3-adamantane diacetic acid polycondensate, 1-3 parts of attapulgite and 1-4 parts of graphene oxide fiber.

Preferably, the preparation method of the phospho-s-triazine hyperbranched macromolecular compound comprises the following steps: adding the s-triazine hyperbranched compound into an organic solvent, then adding chloromethyl phosphoric acid into the organic solvent, stirring and reacting for 4-6 hours at the temperature of 40-60 ℃, then performing rotary evaporation to remove the solvent, washing the crude product for 3-5 times by using diethyl ether, and then performing rotary evaporation to remove the diethyl ether to obtain the phosphate-s-triazine hyperbranched macromolecular compound.

Preferably, the mass ratio of the s-triazinyl hyperbranched compound to the organic solvent to the chloromethyl phosphoric acid is (3-4): (10-15): 1.

Preferably, the s-triazine hyperbranched compound is a second-generation s-triazine hyperbranched compound, and the preparation method is shown in example 1 of the Chinese patent with application number of 201910881075.8.

Preferably, the organic solvent is any one of tetrahydrofuran, N-dimethylformamide, N-dimethylacetamide and N-methylpyrrolidone.

Preferably, the preparation method of the sulfonic diethanolamine/1, 3-adamantane diacetic acid polycondensate comprises the following steps:

step C1, adding diethanolamine, 1, 3-adamantane diacetic acid, dicyclohexyl carbodiimide and 4-dimethylamino pyridine into N-methylpyrrolidone, stirring and reacting for 6-8 hours at 30-50 ℃, then precipitating in water, washing the precipitated polymer with ethanol for 3-7 times, and finally drying in a vacuum drying oven at 80-90 ℃ to constant weight to obtain a diethanolamine/1, 3-adamantane diacetic acid polycondensate;

and step C2, adding the diethanolamine/1, 3-adamantane diacetic acid polycondensate prepared in the step C1 into an ethanol solution of 1, 4-butanesultone, stirring and reacting for 15-20 hours at 50-60 ℃ in the atmosphere of nitrogen or inert gas, then performing rotary evaporation to remove ethanol, washing the product with water for 3-6 times, and finally drying in a vacuum drying oven at 80-90 ℃ to constant weight to obtain the sulfonic diethanolamine/1, 3-adamantane diacetic acid polycondensate.

Preferably, the molar ratio of the diethanol amine, the 1, 3-adamantane diacetic acid, the dicyclohexyl carbodiimide, the 4-dimethylamino pyridine and the N-methyl pyrrolidone in the step C1 is 1:1 (0.4-0.8) to 0.5 (8-14).

Preferably, the mass ratio of the diethanol amine/1, 3-adamantane diacetic acid polycondensate to the ethanol solution of the 1, 4-butanesultone in the step C2 is 1 (5-10).

Preferably, the mass percentage concentration of the ethanol solution of the 1, 4-butanesultone is 15-25%.

Preferably, the inert gas is any one of helium, neon and argon.

Preferably, the particle size of the attapulgite is 300-500 meshes; the length range of the graphene oxide fiber is 3-8 mm, and the diameter of the graphene oxide fiber is 100-400 nm.

Another object of the present invention is to provide a method for preparing the concrete additive, which comprises the following steps: the components are uniformly mixed according to a ratio to obtain a mixture, then the mixture is uniformly mixed with water with the mass being 3-5 times of the mass of the mixture, sodium hydroxide is added into the mixture, the PH value is adjusted to 7, then the mixture is dried, and the mixture is added into a ball mill for grinding for 15-25 minutes and then discharged.

It is still another object of the present invention to provide a concrete using the concrete additive as an additive.

Due to the application of the technical scheme, compared with the prior art, the invention has the following advantages:

(1) according to the preparation method of the concrete additive, the components are uniformly mixed, the PH is adjusted, and the mixture is ground.

(2) The concrete additive provided by the invention overcomes the defects that the concrete additive in the prior art has single function, and the concrete with excellent comprehensive performance can be obtained only by adding a large amount of additives with different weights at the same time, but the addition of a large amount of additives can cause negative effects on different degrees of the setting time and the early and late strength of the concrete due to the caking property problem; the defects that different additives easily generate antagonism; the concrete additive also overcomes the technical problems of poor water reducing effect, large mixing amount, poor plasticizing effect, easy deterioration and poor concrete protection effect existing in the concrete additive on the market more or less, and has the advantages of more excellent water reducing effect, less mixing amount, better environmental protection and plasticizing effect, various functions, more obvious effects of improving the strength, the fluidity, the durability and the impermeability of the concrete material, no negative influence on the comprehensive performance of the concrete, and higher economic value, social value and ecological value.

(3) According to the concrete additive provided by the invention, the graphene oxide fiber is added, and due to more active groups on the graphene oxide fiber, the compatibility of the graphene oxide fiber with other components of concrete is improved, and the addition of the graphene oxide fiber can enable the concrete to be more compact, improve the early strength and effectively improve the durability of the concrete; the addition of the attapulgite can improve the compatibility among the components, further improve the strength of the concrete, can block capillary channels and micro cracks in time, and block and eliminate salt corrosion conditions, so that the impermeability and waterproof performance of the concrete are improved to a greater extent.

(4) According to the concrete additive provided by the invention, the phosphate group-s-triazine hyperbranched macromolecular compound is added, and the molecular structure is firstly hyperbranched, so that the phosphate group-s-triazine hyperbranched macromolecular compound is easier to adsorb on the surface of a concrete material, and a larger steric hindrance is generated among cement particles, and the larger the steric hindrance repulsion force is, the larger the hindrance is to the coagulation among the cement particles, so that the slump of the concrete is kept good; particularly, the triazine organic salt structure is introduced and has synergistic effect with other structures, under the multiple actions of electronic effect, steric effect and conjugate effect, the performance of the triazine organic salt structure is stable and better, the water reducing effect is better, the grain boundary energy of a cement hydration product can be effectively improved, the crystal grain structure of the cement hydration product is refined, the shape of crystal branches is improved, the internal composition of concrete is more compact in a microcosmic manner, the concrete strength is obviously increased in a macroscopic manner, the durability of the concrete is improved, the molecular chain of the component contains more hydrophilic hydroxyl, quaternary ammonium salt base and phosphoric acid, the hydroxyl, quaternary ammonium salt base and phosphoric acid can be adsorbed with water molecules to form a water film, the water film has a good lubricating effect, the flow resistance of the concrete can be reduced, and the fluidity of the cement concrete prepared by machine sand is improved; the molecular chain not only contains a quaternary ammonium salt structure, but also contains a phosphate group structure, so that the component has a certain function of adjusting PH, can effectively prevent the phenomenon of efflorescence inside concrete, and further improves the comprehensive performance of the concrete.

(5) According to the concrete additive provided by the invention, the addition of the sulfo-group diethanol amine/1, 3-adamantane diacetic acid polycondensate can effectively improve the water reducing effect, the sulfamic acid structure is introduced to the side chain of the polycondensate molecule to achieve the water reducing effect, the adamantane structure on the main chain can be favorable for improving the mechanical strength and slump retention due to the steric effect and the electronic effect of the adamantane structure, and the performance stability of the concrete additive can be improved on the whole due to the molecular structure, and the structures have synergistic effect, so that the concrete additive not only plays the role of a water reducing agent, but also has multiple effects of air entraining, antifreezing, delayed coagulation, early strength and the like, the influence and the generated antagonistic effect on the comprehensive performance of concrete caused by the large addition of different additives are effectively avoided, the amount is low, the effect is obvious; and the production and use processes do not contain components which have great influence on the environment, so that the use is safer and more environment-friendly.

Detailed Description

The following detailed description of preferred embodiments of the invention will be made.

The concrete additive is characterized by comprising the following components in parts by weight: 2-5 parts of phosphate s-triazine hyperbranched macromolecular compound, 8-12 parts of sulfonic diethanolamine/1, 3-adamantane diacetic acid polycondensate, 1-3 parts of attapulgite and 1-4 parts of graphene oxide fiber.

Preferably, the preparation method of the phospho-s-triazine hyperbranched macromolecular compound comprises the following steps: adding the s-triazine hyperbranched compound into an organic solvent, then adding chloromethyl phosphoric acid into the organic solvent, stirring and reacting for 4-6 hours at the temperature of 40-60 ℃, then performing rotary evaporation to remove the solvent, washing the crude product for 3-5 times by using diethyl ether, and then performing rotary evaporation to remove the diethyl ether to obtain the phosphate-s-triazine hyperbranched macromolecular compound.

Preferably, the mass ratio of the s-triazinyl hyperbranched compound to the organic solvent to the chloromethyl phosphoric acid is (3-4): (10-15): 1.

Preferably, the s-triazine hyperbranched compound is a second-generation s-triazine hyperbranched compound, and the preparation method is shown in example 1 of the Chinese patent with application number of 201910881075.8.

Preferably, the organic solvent is any one of tetrahydrofuran, N-dimethylformamide, N-dimethylacetamide and N-methylpyrrolidone.

Preferably, the preparation method of the sulfonic diethanolamine/1, 3-adamantane diacetic acid polycondensate comprises the following steps:

step C1, adding diethanolamine, 1, 3-adamantane diacetic acid, dicyclohexyl carbodiimide and 4-dimethylamino pyridine into N-methylpyrrolidone, stirring and reacting for 6-8 hours at 30-50 ℃, then precipitating in water, washing the precipitated polymer with ethanol for 3-7 times, and finally drying in a vacuum drying oven at 80-90 ℃ to constant weight to obtain a diethanolamine/1, 3-adamantane diacetic acid polycondensate;

and step C2, adding the diethanolamine/1, 3-adamantane diacetic acid polycondensate prepared in the step C1 into an ethanol solution of 1, 4-butanesultone, stirring and reacting for 15-20 hours at 50-60 ℃ in the atmosphere of nitrogen or inert gas, then performing rotary evaporation to remove ethanol, washing the product with water for 3-6 times, and finally drying in a vacuum drying oven at 80-90 ℃ to constant weight to obtain the sulfonic diethanolamine/1, 3-adamantane diacetic acid polycondensate.

Preferably, the molar ratio of the diethanol amine, the 1, 3-adamantane diacetic acid, the dicyclohexyl carbodiimide, the 4-dimethylamino pyridine and the N-methyl pyrrolidone in the step C1 is 1:1 (0.4-0.8) to 0.5 (8-14).

Preferably, the mass ratio of the diethanol amine/1, 3-adamantane diacetic acid polycondensate to the ethanol solution of the 1, 4-butanesultone in the step C2 is 1 (5-10).

Preferably, the mass percentage concentration of the ethanol solution of the 1, 4-butanesultone is 15-25%.

Preferably, the inert gas is any one of helium, neon and argon.

Preferably, the particle size of the attapulgite is 300-500 meshes; the length range of the graphene oxide fiber is 3-8 mm, and the diameter of the graphene oxide fiber is 100-400 nm.

Another object of the present invention is to provide a method for preparing the concrete additive, which comprises the following steps: the components are uniformly mixed according to a ratio to obtain a mixture, then the mixture is uniformly mixed with water with the mass being 3-5 times of the mass of the mixture, sodium hydroxide is added into the mixture, the PH value is adjusted to 7, then the mixture is dried, and the mixture is added into a ball mill for grinding for 15-25 minutes and then discharged.

It is still another object of the present invention to provide a concrete using the concrete additive as an additive.

Due to the application of the technical scheme, compared with the prior art, the invention has the following advantages: according to the preparation method of the concrete additive, the components are uniformly mixed, and after the PH is adjusted, the concrete additive is obtained through grinding, the preparation method is simple and easy to implement, convenient to operate and control, high in preparation efficiency and finished product qualification rate, small in equipment dependence and suitable for continuous large-scale production; the concrete additive provided by the invention overcomes the defects that the concrete additive in the prior art has single function, and the concrete with excellent comprehensive performance can be obtained only by adding a large amount of additives with different weights at the same time, but the addition of a large amount of additives can cause negative effects on different degrees of the setting time and the early and late strength of the concrete due to the caking property problem; the defects that different additives easily generate antagonism; the concrete additive also overcomes the technical problems of poor water reducing effect, large mixing amount, poor plasticizing effect, easy deterioration and poor concrete protection effect existing in the concrete additive on the market more or less, and has the advantages of more excellent water reducing effect, less mixing amount, better environmental protection and plasticizing effect, various functions, more obvious effects of improving the strength, the fluidity, the durability and the impermeability of the concrete material, no negative influence on the comprehensive performance of the concrete, and higher economic value, social value and ecological value.

According to the concrete additive provided by the invention, the graphene oxide fiber is added, and due to more active groups on the graphene oxide fiber, the compatibility of the graphene oxide fiber with other components of concrete is improved, and the addition of the graphene oxide fiber can enable the concrete to be more compact, improve the early strength and effectively improve the durability of the concrete; the addition of the attapulgite can improve the compatibility among the components, further improve the strength of the concrete, can block capillary channels and micro cracks in time, and block and eliminate salt corrosion conditions, so that the impermeability and waterproof performance of the concrete are improved to a greater extent; according to the concrete additive provided by the invention, the phosphate group-s-triazine hyperbranched macromolecular compound is added, and the molecular structure is firstly hyperbranched, so that the phosphate group-s-triazine hyperbranched macromolecular compound is easier to adsorb on the surface of a concrete material, and a larger steric hindrance is generated among cement particles, and the larger the steric hindrance repulsion force is, the larger the hindrance is to the coagulation among the cement particles, so that the slump of the concrete is kept good; particularly, the triazine organic salt structure is introduced and has synergistic effect with other structures, under the multiple actions of electronic effect, steric effect and conjugate effect, the performance of the triazine organic salt structure is stable and better, the water reducing effect is better, the grain boundary energy of a cement hydration product can be effectively improved, the crystal grain structure of the cement hydration product is refined, the shape of crystal branches is improved, the internal composition of concrete is more compact in a microcosmic manner, the concrete strength is obviously increased in a macroscopic manner, the durability of the concrete is improved, the molecular chain of the component contains more hydrophilic hydroxyl, quaternary ammonium salt base and phosphoric acid, the hydroxyl, quaternary ammonium salt base and phosphoric acid can be adsorbed with water molecules to form a water film, the water film has a good lubricating effect, the flow resistance of the concrete can be reduced, and the fluidity of the cement concrete prepared by machine sand is improved; the molecular chain not only contains a quaternary ammonium salt structure, but also contains a phosphate group structure, so that the component has a certain function of adjusting PH, can effectively prevent the phenomenon of efflorescence inside concrete, and further improves the comprehensive performance of the concrete.

According to the concrete additive provided by the invention, the addition of the sulfo-group diethanol amine/1, 3-adamantane diacetic acid polycondensate can effectively improve the water reducing effect, the sulfamic acid structure is introduced to the side chain of the polycondensate molecule to achieve the water reducing effect, the adamantane structure on the main chain can be favorable for improving the mechanical strength and slump retention due to the steric effect and the electronic effect of the adamantane structure, and the performance stability of the concrete additive can be improved on the whole due to the molecular structure, and the structures have synergistic effect, so that the concrete additive not only plays the role of a water reducing agent, but also has multiple effects of air entraining, antifreezing, delayed coagulation, early strength and the like, the influence and the generated antagonistic effect on the comprehensive performance of concrete caused by the large addition of different additives are effectively avoided, the amount is low, the effect is obvious; and the production and use processes do not contain components which have great influence on the environment, so that the use is safer and more environment-friendly.

The invention will be further described with reference to specific examples, but the scope of protection of the invention is not limited thereto: