阅读说明：本技术 一种高性能混凝土表面防护剂及其制备方法 (High-performance concrete surface protective agent and preparation method thereof ) 是由 戚城 于 2020-03-02 设计创作，主要内容包括：本发明公开了一种高性能混凝土表面防护剂,其有效成分与溶剂；其中,有效成分主要由小分子硅油、氨基硅烷偶联剂、钾催化剂、烷基三乙氧基硅烷和终止剂制成；溶剂主要由正硅酸乙酯、溶剂油和表面活性剂组成。相应的,本发明还公开了上述高性能混凝土表面防护剂的制备方法。本发明中的高性能混凝土表面防护剂,能够牢固地粘附在混凝土的表面和毛细孔道中,使得亲水的混凝土表面和毛细孔隙变为疏水表面,从而减少氯离子、强酸、强碱等腐蚀介质的侵蚀,对高性能混凝土形成良好的保护作用。(The invention discloses a high-performance concrete surface protective agent, which comprises effective components and a solvent; wherein, the effective components are mainly prepared from micromolecular silicone oil, amino silane coupling agent, potassium catalyst, alkyl triethoxy silane and terminating agent; the solvent mainly comprises ethyl orthosilicate, solvent oil and surfactant. Correspondingly, the invention also discloses a preparation method of the high-performance concrete surface protective agent. The high-performance concrete surface protective agent disclosed by the invention can be firmly adhered to the surface and the capillary channels of concrete, so that the hydrophilic concrete surface and capillary pores are changed into hydrophobic surfaces, thus the corrosion of corrosive media such as chloride ions, strong acid, strong alkali and the like is reduced, and a good protective effect is formed on the high-performance concrete.)

1. The high-performance concrete surface protective agent is characterized by comprising effective components and a solvent in a weight ratio of 1: 1-3, wherein the effective components are mainly prepared from the following raw materials in parts by weight:

the solvent is prepared from the following raw materials in parts by weight:

5-15 parts of ethyl orthosilicate;

75-85 parts of solvent oil;

2-10 parts of a surfactant.

2. The high-performance concrete surface protective agent according to claim 1, wherein the small molecular silicone oil is one or more of methyl silicone oil, ethyl silicone oil, phenyl silicone oil, hydrogen-containing silicone oil, hydroxyl silicone oil, methyl ethoxy silicone oil, methyl phenyl silicone oil and methyl trifluoro propyl silicone oil;

the alkyl triethoxysilane is isobutyl triethoxysilane and/or isooctyl triethoxysilane.

3. The high-performance concrete surface protective agent according to claim 1 or 2, wherein the small molecule silicone oil is selected from hydrogen-containing silicone oil and/or hydroxyl silicone oil;

the alkyl triethoxysilane is isooctyl triethoxysilane.

4. The high performance concrete surface protective agent according to claim 1, wherein the solvent is selected from D40 solvent oil, D60 solvent oil or D80 solvent oil;

the surfactant is selected from diisooctyl succinate sodium sulfonate and/or diiso-alkyl succinate sodium sulfonate.

5. The high-performance concrete surface protective agent according to claim 1 or 4, wherein the solvent oil is D40 solvent oil;

the weight ratio of the ethyl orthosilicate to the solvent oil is as follows: 1: (6-10).

6. The high performance concrete surface protectant according to claim 1, wherein the active ingredients further comprise:

1-5 parts of a preservative.

7. The high performance concrete surface protectant of claim 6, wherein said preservative is selected from the group consisting of calcium nitrite, 1-butyl-3-methylimidazolium tetrafluoroborate, and ethanolamine.

8. The high performance concrete surface protectant according to claim 6 or claim 7, wherein said preservative is ethanolamine.

9. The high performance concrete surface protectant according to claim 1, wherein the potassium catalyst is prepared by stirring and heating potassium hydroxide and hydrogen-containing silicone oil at 110-125 ℃ for 30min, and the potassium catalyst contains 0.1-1% of potassium hydroxide.

10. A method for preparing the high performance concrete surface protective agent according to any one of claims 1 to 9, comprising:

(1) putting 85-94 parts of micromolecular silicone oil, 2-10 parts of amino silane coupling agent and 0.1-0.5 part of potassium catalyst into a reaction kettle, and heating and stirring at 90-110 ℃ for 4-8 hours to obtain an intermediate product;

(2) cooling to 80-90 ℃, adding 3-12 parts of alkyl triethoxysilane into the reaction kettle, stirring for reaction for 1-2.5 hours, and adding 0.1-0.5 part of terminator for neutralization to obtain the effective components of the high-performance concrete protective agent;

(3) and cooling the effective components to room temperature, adding tetraethoxysilane, a surfactant and solvent oil, and uniformly mixing to obtain a finished product of the high-performance concrete surface protective agent.

Technical Field

The invention relates to the technical field of high-performance concrete surface protection, in particular to a high-performance concrete surface protective agent and a preparation method thereof.

Background

The high-performance concrete is a novel cement-based composite material with high strength, low brittleness and high durability. The cement mortar mainly comprises fine sand, cement, quartz powder, silica fume, a high-efficiency water reducing agent and the like. Meanwhile, a small amount of micro steel fibers are often blended for improving the performance. The particle size of the raw materials adopted by the high-performance concrete is much smaller than that of the common concrete, and is generally controlled below 1mm, so that the pores of the high-performance concrete are relatively small. Due to its excellent properties, high performance concrete is gradually used in the fields of building construction and infrastructure construction (such as bridges, roads, tunnels) in a wide range. However, since concrete is easily deteriorated by physical, chemical and biological actions of the surrounding environment, and the life of a building structure is shortened, a surface protective agent is often used to protect the surface of high-performance concrete in the prior art.

At present, the concrete protection mainly adopts a surface coating method, for example, asphalt, polyurethane, epoxy resin, acrylic acid, ethylene rubber or greening rubber and other coatings are covered on the concrete surface, and the coatings have strong alkali resistance and strong adhesive force, but can completely seal the gaps on the concrete surface, organize the volatilization of water in the concrete, and are difficult to achieve the optimal protection effect. The novel protective agent such as silane protective agent mainly represents alkyl triethoxysilane, and can permeate into the concrete, thereby effectively reducing the water absorption of the capillary pores of the concrete and playing a role in protection. However, the penetration depth of the protective agent is shallow, the chloride absorption capacity is low, and the protective performance is poor.

The other novel protective agent is a silane protective paste, such as the silane protective paste developed in Chinese patent CN101115696, the viscosity of the silane protective paste is less than or equal to 100mPa · s, the silane protective paste can be used for hydrophobic treatment of concrete, the coating amount of the silane paste can reach more than 1mm, and the silane protective paste can stay on the surface of the concrete for a long time, so that the concrete can fully react and permeate with the protective agent, but the protective agent has high cost and slow reaction speed, and is difficult to be applied in some occasions.

Disclosure of Invention

The technical problem to be solved by the invention is to provide a high-performance concrete surface protective agent which can be effectively combined with high-performance concrete, has good defense capability against corrosive substances and microorganisms, and can be quickly constructed.

In order to solve the technical problems, the invention provides a high-performance concrete surface protective agent which is characterized by comprising effective components and a solvent in a weight ratio of 1: 1-3, wherein the effective components are mainly prepared from the following raw materials in parts by weight:

the solvent is prepared from the following raw materials in parts by weight:

5-15 parts of ethyl orthosilicate;

75-85 parts of solvent oil;

2-10 parts of a surfactant.

As an improvement of the technical scheme, the micromolecular silicone oil is one or more of methyl silicone oil, ethyl silicone oil, phenyl silicone oil, hydrogen-containing silicone oil, hydroxyl silicone oil, methyl ethoxy silicone oil, methyl phenyl silicone oil and methyl trifluoro propyl silicone oil;

the alkyl triethoxysilane is isobutyl triethoxysilane and/or isooctyl triethoxysilane.

As an improvement of the technical scheme, the micromolecular silicone oil is selected from hydrogen-containing silicone oil and/or hydroxyl silicone oil;

the alkyl triethoxysilane is isooctyl triethoxysilane.

As an improvement of the technical scheme, the solvent is D40 solvent oil, D60 solvent oil or D80 solvent oil;

the surfactant is selected from diisooctyl succinate sodium sulfonate and/or diiso-alkyl succinate sodium sulfonate.

As an improvement of the technical scheme, the solvent oil is D40 solvent oil;

the weight ratio of the ethyl orthosilicate to the solvent oil is as follows: 1: (6-10).

As an improvement of the above technical solution, the active ingredients further include:

1-5 parts of a preservative.

As an improvement of the technical scheme, the preservative is selected from calcium nitrite, 1-butyl-3-methylimidazolium tetrafluoroborate or ethanolamine.

As an improvement of the technical scheme, the preservative is ethanolamine.

As an improvement of the technical scheme, the potassium catalyst is prepared by stirring and heating potassium hydroxide and hydrogen-containing silicone oil at 110-125 ℃ for 30min, and the potassium catalyst contains 0.1-1% of potassium hydroxide.

Correspondingly, the invention also discloses a preparation method of the high-performance concrete surface protective agent, which comprises the following steps:

(1) putting 85-94 parts of micromolecular silicone oil, 2-10 parts of amino silane coupling agent and 0.1-0.5 part of potassium catalyst into a reaction kettle, and heating and stirring at 90-110 ℃ for 4-8 hours to obtain an intermediate product;

(2) cooling to 80-90 ℃, adding 3-12 parts of alkyl triethoxysilane into the reaction kettle, stirring for reaction for 1-2.5 hours, and adding 0.1-0.5 part of terminator for neutralization to obtain the effective components of the high-performance concrete protective agent;

(3) and cooling the effective components to room temperature, adding tetraethoxysilane, a surfactant and solvent oil, and uniformly mixing to obtain a finished product of the high-performance concrete surface protective agent.

The implementation of the invention has the following beneficial effects:

1. according to the invention, micromolecular silicone oil and alkyl triethoxysilane are used as active components, wherein the micromolecular silicone oil has excellent penetration effect and can quickly penetrate into micro gaps of high-performance concrete; the alkyl triethoxysilane and the micromolecule silicone oil can be condensed to form reticular organic silicon resin under the action of the catalyst, and the reticular organic silicon resin is firmly adhered to the surface and capillary channels of the concrete, so that the hydrophilic surface and capillary pores of the concrete are changed into hydrophobic surfaces, and the corrosion of corrosive media such as chloride ions, strong acid, strong alkali and the like is reduced; meanwhile, the surface protective agent in the invention can not block the tiny pores of the high-performance concrete, can not prevent the water in the concrete from volatilizing, and ensures the air permeability of the high-performance concrete.

2. The solvent in the invention comprises tetraethoxysilane and solvent oil; wherein, the tetraethoxysilane can be hydrolyzed in situ to form silica sol with higher viscosity; the viscosity of the miscella is relatively low; the combination of the two can promote the penetration of the surface protective agent to the high-performance concrete in the early stage and can have the surface protective agent in the later stageEffectively preventing the surface protective agent from falling off. At the same time, the silica sol can be mixed with Ca (OH) produced by hydration₂And the reaction reduces concrete carbonization.

3. The protective agent also contains a preservative, which can effectively prevent the corrosion of steel fibers in the high-performance concrete and further influence the performance of the high-performance concrete.

Drawings

FIG. 1 is a flow chart of a method for preparing a high-performance concrete surface protective agent according to the invention.

Detailed Description

In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention will be described in further detail with reference to the accompanying drawings.

The invention provides a high-performance concrete surface protective agent which comprises effective components and a solvent in a weight ratio of 1: 1-3.

The active ingredients are mainly prepared from the following raw materials in parts by weight:

the solvent is prepared from the following raw materials in parts by weight:

5-15 parts of ethyl orthosilicate;

75-85 parts of solvent oil;

2-10 parts of a surfactant.

Wherein, the micromolecular silicone oil can be one or more of alkyl silicone oil, hydrogen-containing silicone oil, hydroxyl silicone oil, alkyl ethoxy silicone oil and alkyl vinyl silicone oil, but is not limited to the above; specifically, the alkyl silicone oil includes methyl silicone oil, ethyl silicone oil, but is not limited thereto; the hydrogen-containing silicone oil includes methyl hydrogen-containing silicone oil, ethyl hydrogen-containing silicone oil or hydroxy silicone oil, but is not limited thereto; the hydroxyl silicone oil includes methyl hydroxyl silicone oil or ethyl hydroxyl silicone oil, but is not limited thereto; the alkyl ethoxy silicone oil includes, but is not limited to, methyl ethoxy silicone oil; the alkyl vinyl silicone oil includes, but is not limited to, methyl vinyl silicone oil.

Preferably, the hydrogen-containing silicone oil is selected, has strong reaction activity, can be self-condensed under the catalysis of a potassium catalyst and alkali in concrete or is condensed with alkyl triethoxy to form a three-dimensional network structure, and enhances the corrosion resistance and durability of high-performance concrete. Further preferably, methyl hydrogen silicone oil is selected.

The alkyl triethoxysilane is isobutyl triethoxysilane and/or isooctyl triethoxysilane; the alkyl triethoxysilane has good hydrophobic and waterproof properties, and when applied to the surface of high performance concrete, the alkoxy groups are hydrolyzed and condensed to form a network film, thereby providing protection. Preferably, isooctyltriethoxysilane is selected, which has better stability, low volatility and higher content of the effective substances after condensation.

It should be noted that in the prior art, isooctyltriethoxysilane is generally applied in the form of a paste, which increases or prolongs the residence time on the concrete surface, thereby allowing the penetration of the protective agent to be deeper and more complete. However, the penetration depth of the paste is shallow in a short time, and particularly, the penetration depth is shallow on the surface of high-performance concrete with small pores. Therefore, the micromolecular silicone oil is introduced into the formula, so that the penetration speed of the protective agent can be increased, the protective agent can be penetrated into high-performance concrete micro pores in a short time, and the protective effect is achieved.

Wherein, the aminosilane coupling agent is one or a combination of aminosilane, aminomethyl silane, aminoethyl aminopropyl silane and aminoethyl aminopropyl methyl silane; the amino silane coupling agent can react with micromolecular silicone oil to form an amino-blocked organic silicon molecular chain, and the adhesive force of the surface protective agent to the surface of high-performance concrete is enhanced.

Wherein the potassium catalyst is prepared by stirring and heating potassium hydroxide and hydrogen-containing silicone oil at the temperature of 110-125 ℃ for 30min, and the potassium catalyst contains 0.1-1% of potassium hydroxide.

Wherein the terminating agent is an acidic reagent capable of reacting with the organic base catalyst to remove the remaining organic base catalyst, thereby terminating the reaction for producing the active ingredient. The terminator can be one or more of hydrochloric acid, sulfuric acid, acetic acid or oxalic acid.

In the solvent formula of the invention, the solvent oil can be D40 solvent oil, D60 solvent oil or D80 solvent oil; preferably, D40 mineral spirit is used. The D40 solvent oil has strong dissolving power and good stability, and does not release toxic gas. And the viscosity of the D40 solvent oil is low, so that the overall viscosity of the surface protective agent is low, and the surface protective agent can quickly permeate into the interior of the base material along the tiny pores of the base material after being applied to the surface of the high-performance concrete base material to form a protective effect.

On the other hand, the solvent formula of the invention also contains ethyl orthosilicate which can generate in-situ hydrolysis reaction after being applied to the surface of concrete to form silica sol, and the silica sol has higher viscosity and can effectively prevent the surface protective agent from dropping due to the action of gravity in the later stage of reaction. When the weight part of the tetraethoxysilane is more than 15 parts, the viscosity at the later period is too high, so that the surface protective agent is not favorably permeated into high-performance concrete. When the weight part of the tetraethoxysilane is less than 5 parts, the surface protective agent is easy to drip.

Meanwhile, the ethyl silicate can be hydrated with high-performance concrete to form Ca (OH)₂Reacting to generate a gel material, and compacting the high-performance concrete; and also prevents carbonization of the high performance concrete.

Further, in order to ensure the permeability of the surface protective agent, the weight ratio of the tetraethoxysilane to the solvent oil is controlled as follows: 1: (6-10); preferably, the ratio of ethyl orthosilicate: 1, (6-8). Through the coordination effect of the solvent, the viscosity of the surface protective agent is 5-20 mPa · s, the surface protective agent has excellent adhesion to the surface of a high-performance concrete matrix, and the protective effect can be achieved only by brushing once. Specifically, the surface protective agent can be applied to the surface of the high-performance concrete by means of coating such as rolling, brushing, spraying or soaking.

Wherein the surfactant is anionic surfactant, specifically, succinic acid sodium salt; more specifically, diisooctyl sulfosuccinate and/or diisoalkyl sulfosuccinate may be used, but not limited thereto.

Further, the surface protective agent also comprises the following components:

1-5 parts of a preservative.

The preservative can effectively prevent corrosion of micro steel fibers in the high-performance concrete matrix, and further influences the performance of the high-performance concrete. Specifically, the preservative can be selected from calcium nitrite, 1-butyl-3-methylimidazolium tetrafluoroborate or ethanolamine; preferably, ethanolamine is selected. The ethanolamine has little influence on the performance of the surface protective agent and can not react with other components.

Correspondingly, referring to fig. 1, the invention also discloses a preparation method of the high-performance concrete surface protective agent, which comprises the following steps:

s1: putting 85-94 parts of micromolecular silicone oil, 2-10 parts of amino silane coupling agent and 0.1-0.5 part of potassium catalyst into a reaction kettle, and heating and stirring at 90-110 ℃ for 4-8 hours to obtain an intermediate product;

specifically, the micromolecular silicone oil reacts with the aminosilane coupling agent under the catalysis of a potassium catalyst to form an amino-block organic silicon molecular chain, so that the adhesive force of the surface protective agent to the surface of the high-performance concrete is enhanced.

S2: cooling to 80-90 ℃, adding 3-12 parts of alkyl triethoxysilane into the reaction kettle, stirring for reaction for 1-2.5 hours, and adding 0.1-0.5 part of terminator for neutralization to obtain the effective components of the high-performance concrete protective agent;

after the alkyl triethoxysilane is added, the alkyl triethoxysilane can further react with small molecular silicone oil and an aminosilane coupling agent to form a reticular organic silicon resin. After coating, the organic silicon resin can be firmly adhered to the surface and capillary channels of concrete, so that the hydrophilic concrete surface and capillary pores are changed into a hydrophobic surface, and the corrosion of chloride ions is reduced; meanwhile, the surface protective agent in the invention can not block the tiny pores of the high-performance concrete, can not prevent the water in the concrete from volatilizing, and ensures the air permeability of the high-performance concrete.

S3: and cooling the effective components to room temperature, adding tetraethoxysilane, a surfactant and solvent oil, and uniformly mixing to obtain a finished product of the high-performance concrete surface protective agent.

The invention is further illustrated by the following specific examples.