Two-component quick-hardening material and method for producing same

Abstract

The present application relates to the surface treatment technology of cement-based materials, aiming to provide a two-component quick hardening material and a preparation method thereof. The material is composed of component A and component B; wherein the component A is a stable liquid polysilane prepared by hydrolysis condensation reaction of silane, hydrogen ion donor, alcohol and appropriate amount of deionized water, and a hydrogen ion acceptor is also added during the reaction; the component B is a catalyst mixed by organotin, carbon-based compound and solvent. The product of the present application has a faster reaction rate than the water-based silicate type hardening material, a more significant wear resistance effect and a better durability; has a better storage stability, ensures that the cement-based material still has good permeability after long-term storage, thereby stably improving the performance and continuously maintaining, and can well adapt to the transportation and storage requirements of remote construction sites.

Description

Technical Field

[0001] The invention belongs to the surface treatment technology of cement-based materials, and particularly relates to a two-component fast-hardening material and a preparation method thereof. Background Art

[0002] In response to the increasing demand for wear-resistant, non-slip, beautiful and clean floors in current construction facilities, researchers at home and abroad have developed a variety of hardening materials for cement-based floors. By further enhancing the internal density of cement, they can reduce the problems of sanding and alkali efflorescence that are prone to occur in traditional cement-based floors.

[0003] Currently, the main design approaches for hardening materials fall into two categories: one uses silicate solutions as the primary component, such as the one disclosed in patent document CN 202311409310.4, which uses potassium and sodium methyl silicate as the primary components. By adding additives such as nano-silica sol and modified graphene, the materials improve the surface density, hardness, impermeability, and durability of concrete building panels, addressing issues such as looseness, dusting, sanding, and peeling. The other uses nano-silica sol as the primary component, such as patent documents CN 201410172177.X and CN 201010543000.8, which disclose silica sol as the primary component, with catalysts, surfactants, and other additives added. These materials are then directly sprayed onto the concrete surface to achieve high wear resistance, high hardness, high water repellency, and dust control. The advantages of these two types of hardening materials lie in their strong permeability, allowing them to quickly penetrate the pores of concrete. However, their surface effects are less pronounced, as their hardening reaction with cement is slow, resulting in a less pronounced cross-linked network structure on the surface. In addition, because it easily reacts with air or itself, resulting in a decrease in storage stability, the hardness and wear resistance of the concrete surface will gradually decrease with the extension of usage time, and the durability will be significantly deteriorated.

[0004] With the increasing demand for hardness, wear resistance, and other durability in medium- and heavy-load industrial sites such as factories, garages, and logistics warehouses, penetration-hardening materials are now required to provide excellent stability, rapid hardening, and long-term durability. Therefore, developing a flooring material that can rapidly improve the overall performance of concrete substrates while also meeting durability requirements has become a research priority for researchers in this field. Summary of the Invention

[0005] The technical problem to be solved by the present invention is to overcome the deficiencies in the prior art and provide a two-component fast-hardening material and a preparation method thereof.

[0006] In order to solve the above technical problems, the solution adopted by the present invention is:

[0007] Provided is a two-component rapid hardening material, which is composed of component A and component B; wherein,

[0008] Component A is a stable liquid polysilane prepared by hydrolysis-condensation reaction of silane, a hydrogen ion donor, an alcohol, and an appropriate amount of deionized water. The mass ratio of silane: hydrogen ion donor: alcohol is 30-50:0.0001-0.05:1-3. A hydrogen ion acceptor is also added during the reaction, accounting for 3-5‰ of the mass of the silane.

[0009] Component B is a catalyst prepared by mixing organic tin, carbon-based compound and solvent, wherein the mass ratio of organic tin: carbonyl compound: solvent is 1:1:0-100.

[0010] As a preferred embodiment of the present invention, the silane contains at least one of the following alkoxy functional groups: tetraalkoxy functional group Si(OR1)(OR2)(OR3)(OR4), trialkoxy functional group Si(OR1)(OR2)(OR3)R4, dialkoxy functional group Si(OR1)(OR2)R3R4 or monoalkoxy functional group Si(OR1)R2R3R4, wherein R1, R2, R3, and R4 are hydrogen or an alkyl group with 1 to 16 carbon atoms.

[0011] As a preferred embodiment of the present invention, the hydrogen ion donor is one of HCl, H2SO4, HNO3, and CH3COOH.

[0012] As a preferred embodiment of the present invention, the alcohol is one of methanol, ethanol, and isopropanol, or a mixture of two or all three.

[0013] As a preferred embodiment of the present invention, the hydrogen ion acceptor is one of CaCO3, Al(OH)3, and SrCO3.

[0014] As a preferred embodiment of the present invention, the organotin is one of tetrabutyltin, dibutyltin diacetate and dibutyltin dilaurate.

[0015] As a preferred embodiment of the present invention, the carbon-based compound is one of dibenzoyl, benzophenone, benzoin, benzoin ethyl ether, and benzoin butyl ether.

[0016] As a preferred embodiment of the present invention, the solvent is one of methanol, ethanol, and isopropanol, or a mixture of at least two of them.

[0017] The present invention further provides a method for preparing the aforementioned two-component rapid hardening material, comprising the following steps:

[0018] (1) Weigh the raw materials of component A and component B according to the mass ratio;

[0019] (2) First, deionized water, alcohol, hydrogen ion donor, and silane are added to the first reaction vessel in sequence, and stirred at 300-800 rpm for 1-5 hours at an oil bath temperature of 40-90°C; then, a hydrogen ion acceptor is added, and the mixture is condensed and refluxed at an oil bath temperature of 60-100°C while stirring at 300-800 rpm for 4-12 hours to carry out a hydrolysis-condensation reaction; after the reaction is completed, the mixture is cooled to room temperature, and the product is filtered through filter paper to obtain a filtrate, which is component A, which is sealed for later use;

[0020] (2) Add the organotin, carbon-based compound and solvent into a second reaction vessel, and stir at 200-500 rpm for 10-60 min at room temperature; the obtained mixed solution is component B, which is sealed for later use.

[0021] The present invention further provides a method for using the aforementioned two-component rapid hardening material, comprising the following steps:

[0022] (1) Carry out the construction and maintenance of concrete floor according to the requirements of the construction plan;

[0023] (2) At room temperature, mix the liquid of component A and the liquid of component B in a mass ratio of 97:3; then apply the mixture on the surface of the floor after curing, with the amount of the mixture used being 10-20g / m2;

[0024] (3) Continue drying at room temperature for 8 hours to form a hardened material layer on the surface of the floor, and finally obtain a cement-based floor with a hardened material layer.

[0025] Compared with the prior art, the technical effects of the present invention are:

[0026] 1. The two-component rapid-hardening material provided by this invention has a faster reaction rate than water-based silicate-based penetrating hardening materials. The carbon-based compound in this invention forms a cation under the influence of a hydrogen ion donor. After losing water molecules, it forms a stable cation, which reacts with alcohols to form a conjugate acid, forming a catalyst that accelerates the reaction rate of the system. This catalyst enables the silane in component A to react and cure rapidly, resulting in more complete hydrolysis of the silane and improved 24-hour surface water absorption performance of the cement-based material.

[0027] 2. The two-component fast-hardening material provided by the present invention has more significant wear resistance and better durability than water-based silicate penetrating hardening materials. Among them, component A is a polysilane formed by the hydrolysis and condensation reaction of silane, and component B is a catalyst. Components A and B are simply mixed and applied to the surface of the cement-based material. Under the action of the catalyst, the polysilane accelerates its own polycondensation reaction while reacting with calcium hydroxide, calcium silicate hydrate, etc. in the cement, and finally fills the surface pores of the cement-based material by forming high-density calcium silicate hydrate and silicon dioxide particles, forming a high-density surface structure. By controlling the polysilane raw materials, reaction conditions and the mass ratio with the catalyst, the formed surface structure has excellent performance in terms of hardness, glossiness, permeability, etc. Compared with water-based silicate penetrating hardening materials, the two-component polysilane hardening material does not introduce additional metal cations, reduces the possibility of surface alkali and alkali-aggregate reaction, and increases the service life. In addition, the surface color of the cement-based material treated with polysilane does not change before and after treatment.

[0028] 3. The technical solution provided by the present invention is two-component separation and storage, and a hydrogen ion receptor neutralization reaction is added during the preparation of polysilane, and the hydrogen ions introduced by silane during the hydrolysis and condensation reaction are effectively removed through precise control. On the one hand, it prevents the hydrogen ions in the hardening material from reacting with the alkaline substances in the cement-based material to generate water, resulting in the formation of pores and the liberation of metal cations. On the other hand, it reconciles and balances the acid-base environment in the solution to keep the hydrolysis and condensation reaction of polysilane in a balanced state, preventing the increase in viscosity or even complete stagnancy caused by the irreversible curing reaction of polysilane. Compared with other organosilicon-based penetrating hardening materials, it has better storage stability, ensuring good permeability to cement-based materials after long-term storage, thereby steadily improving its performance and maintaining it continuously.

[0029] 4. The reaction mechanism of the present invention differs from the conventional two-component hardeners that use organotin catalysts to catalyze the hydrolysis and polycondensation of polysilane. Conventional techniques use organotin catalysts to promote the reaction between silane and epoxy resin; however, the present invention adds an organotin catalyst to accelerate the hydrolysis and condensation of silane, enabling a more complete reaction between the generated silane and concrete, thereby accelerating the reaction rate between the hardened material and concrete. This also results in superior properties such as higher surface hardness and 24-hour surface water absorption. Therefore, the catalyst's target of action and the resulting technical effects are different.

[0030] 5. The present invention promotes the reaction between components A and B by adding a carbon-based compound. Furthermore, by using a hydrogen ion acceptor to control the reaction rate, the resulting hardener exhibits long-term storage stability, specifically, a shelf life of over a year. Therefore, the product of the present invention is well suited to the transportation and storage needs of construction sites in remote areas. DETAILED DESCRIPTION

[0031] Part I: Implementation of the Invention

[0032] 1. Components of two-component hardening materials:

[0033] The two-component rapid hardening material of the present invention is composed of component A and component B; wherein,

[0034] Component A is a stable liquid polysilane prepared by hydrolysis-condensation reaction of silane, a hydrogen ion donor, an alcohol, and an appropriate amount of deionized water. The mass ratio of silane: hydrogen ion donor: alcohol is 30-50: 0.0001-0.05: 1-3. A hydrogen ion acceptor is added during the reaction, accounting for 3-5‰ of the mass of the silane. The silane contains at least one of the following alkoxy functional groups: tetraalkoxy functional group Si(OR1)(OR2)(OR3)(OR4), trialkoxy functional group Si(OR1)(OR2)(OR3)R4, dialkoxy functional group Si(OR1)(OR2)R3R4, or monoalkoxy functional group Si(OR1)R2R3R4, wherein R1, R2, R3, and R4 are hydrogen or an alkyl group of 1 to 16 carbon atoms. The alcohol is one of methanol, ethanol, and isopropanol, or a mixture of two or all of the three. The hydrogen ion acceptor is one of CaCO3, Al(OH)3, and SrCO3.

[0035] The hydrogen ion donor is one of HCl, H2SO4, HNO3, and CH3COOH. When used, diluted acid solution is used, and the mass of the hydrogen ion donor contained is converted according to the concentration of the acid solution.

[0036] Component B is a catalyst composed of a mixture of an organotin, a carbon-based compound, and a solvent, wherein the mass ratio of organotin:carbonyl compound:solvent is 1:1:0-100. The organotin is one of tetrabutyltin, dibutyltin diacetate, and dibutyltin dilaurate. The carbon-based compound is one of dibenzoyl, benzophenone, benzoin, benzoin ethyl ether, and benzoin butyl ether. The solvent is one of methanol, ethanol, and isopropyl alcohol, or a mixture of at least two of them.

[0037] The reagents used in the present invention can be directly commercially available or prepared according to existing public literature. The present invention does not make any special requirements on the preparation process of the reagents themselves.

[0038] 2. Preparation method of two-component hardening material

[0039] In the present invention, the two-component hardening material is prepared according to the following steps:

[0040] (1) Weigh the raw materials of component A and component B according to the above mass ratio;

[0041] (2) First, deionized water, alcohol, hydrogen ion donor, and silane are added to the first reaction vessel in sequence, and stirred at 300-800 rpm for 1-5 hours at an oil bath temperature of 40-90°C; then, a hydrogen ion acceptor is added, and the mixture is condensed and refluxed at an oil bath temperature of 60-100°C while stirring at 300-800 rpm for 4-12 hours to carry out a hydrolysis-condensation reaction; after the reaction is completed, the mixture is cooled to room temperature, and the product is filtered through filter paper to obtain a filtrate, which is component A, which is sealed for later use;

[0042] (2) Add the organotin, carbon-based compound and solvent into a second reaction vessel, and stir at 200-500 rpm for 10-60 min at room temperature; the obtained mixed solution is component B, which is sealed for later use.

[0043] 3. How to use two-component hardening materials

[0044] As an example, the method for using the two-component hardening material of the present invention includes the following steps:

[0045] (1) Carry out the construction and maintenance of concrete floor according to the requirements of the construction plan;

[0046] (2) At room temperature, mix the liquid of component A and the liquid of component B in a mass ratio of 97:3; then apply the mixture on the surface of the floor after curing, with the amount of the mixture used being 10-20g / m2;

[0047] (3) Continue drying at room temperature for 8 hours to form a hardened material layer on the surface of the floor, and finally obtain a cement-based floor with a hardened material layer.

[0048] Part II Examples and Comparative Examples

[0049] Examples 1-5 were all carried out in accordance with the contents described in the first section to prepare the hardened material. The process parameters of each example are shown in Table 1.

[0050] Table 1

[0051]

[0052]

[0053] Comparative Example 1

[0054] The infiltration nano-hardener includes the following components in percentage by mass: 18.0% to 18.5% of potassium methyl silicate, 48.0% to 48.5% of sodium methyl silicate, 3% to 3.5% of alcoholamine-modified graphene, 6% to 6.5% of nano-Al2O3 sol and 0.5% to 1.0% of surfactant, with the balance being deionized water; wherein the mass ratio of the alcoholamine to the graphene is 1:0.1 to 0.3.

[0055] Comparative Example 2

[0056] The commercially available hardener product model is PC-40, which includes two components, A and B. Among them, component A is composed of silane prepolymer, wear-resistant modification material, stabilizer and solvent; component B is composed of catalyst and solvent; the solvent in both components is ethanol.

[0057] Part III Performance Test and Result Analysis of Products in Examples and Comparative Examples

[0058] 1. Test method

[0059] (1) Prepare mortar samples according to the provisions of JC / T2158-2021;

[0060] (2) According to the provisions of GB / T 22374-2018 Floor Coating Materials, conduct onset time and glossiness (60°) tests;

[0061] (3) According to the provisions of JC / T2158-202, the surface hardness, wear resistance and 24h surface water absorption tests are carried out.

[0062] 2. Test results and analysis

[0063] Based on the same test method, the performance test parameters of the products in Examples 1-5 and Comparative Examples 1-2 are shown in Table 2.

[0064] Table 2

[0065] sample Example 1 Example 2 Example 3 Example 4 Example 5 Comparative Example 1 Comparative Example 2 Surface hardness 3.9 4.1 4.0 3.9 3.9 4.5 4.4 Wear resistance / mm (wear resistance) 0.01 0.002 0.005 0.01 0.002 0.01 0.015 Effective storage time More than 1 year More than 1 year More than 1 year More than 1 year More than 1 year 6 months 6 months Onset time ＜10h ＜10h ＜10h <10h ＜24h 24h 24h Glossiness / ° 66 74 67 65 66 60 58 24h surface water absorption / mm 1.0 1.2 1.5 1.5 1.5 1.9 2

[0066] In Table 1, the onset time refers to the time it takes for the hardened material layer to form; a shorter time indicates a faster hardening rate. A lower 24-hour surface water absorption value indicates better waterproofing and anti-penetration capabilities. The data in Table 1 demonstrates that Examples 1-5 all exhibit optimal performance, primarily manifested in higher surface hardness and wear resistance, as well as superior 24-hour surface water absorption. Furthermore, all examples demonstrate superior performance compared to the control group.

Claims

1. A two-component fast-hardening material, characterized in that: It is composed of component A and component B; Component A is a stable liquid polysilane prepared by hydrolysis-condensation reaction of silane, a hydrogen ion donor, an alcohol, and an appropriate amount of deionized water. The mass ratio of silane: hydrogen ion donor: alcohol is 30-50: 0.0001-0.05: 1-3. A hydrogen ion acceptor is also added during the reaction, accounting for 3-5‰ of the mass of the silane. The silane contains at least one of the following alkoxy functional groups: a tetraalkoxy functional group Si(OR1)(OR2)(OR3)(OR4), a trialkoxy functional group Si(OR1)(OR2)(OR3)R4, a dialkoxy functional group Si(OR1)(OR2)R3R4 or a monoalkoxy functional group Si(OR1)R2R3R4, wherein R1, R2, R3 and R4 are hydrogen or an alkyl group with 1 to 16 carbon atoms; the hydrogen ion donor is one of HCl, H2SO4, HNO3 and CH3COOH; and the hydrogen ion acceptor is one of CaCO3, Al(OH)3 and SrCO3; Component B is a catalyst prepared by mixing an organic tin, a carbon-based compound and a solvent, wherein the mass ratio of the organic tin: the carbonyl compound: the solvent is 1:1:0-100; the carbon-based compound is one of dibenzoyl, benzophenone, benzoin, benzoin ethyl ether and benzoin butyl ether.

2. The two-component fast-hardening material according to claim 1, characterized in that: The alcohol is one of methanol, ethanol and isopropanol, or a mixture of two or three of them.

3. The two-component fast-hardening material according to claim 1, characterized in that: The organic tin is one of tetrabutyltin, dibutyltin diacetate and dibutyltin dilaurate.

4. The two-component fast-hardening material according to claim 1, characterized in that: The solvent is one of methanol, ethanol and isopropanol or a mixture of at least two of them.

5. The method for preparing the two-component rapid hardening material according to claim 1, characterized in that: The following steps are involved: (1) Weigh the raw materials of component A and component B according to the mass ratio; (2) First, deionized water, alcohol, hydrogen ion donor, and silane are added to the first reaction vessel in sequence, and stirred at 300-800 rpm for 1-5 h at an oil bath temperature of 40-90 °C. Then, a hydrogen ion acceptor is added, and the mixture is condensed and refluxed at an oil bath temperature of 60-100 °C while stirring at 300-800 rpm for 4-12 h to carry out a hydrolysis-condensation reaction. After the reaction is completed, the mixture is cooled to room temperature, and the filtrate obtained by filtering the product with filter paper is component A, which is sealed for later use. (2) Add the organotin, carbon-based compound and solvent into the second reaction vessel and stir at 200-500 rpm for 10-60 min at room temperature; the obtained mixed solution is component B, which is sealed for later use.

6. The method for using the two-component rapid hardening material according to claim 1, characterized in that: The following steps are involved: (1) Carry out the construction and maintenance of concrete floor according to the requirements of the construction plan; (2) At room temperature, mix the liquid of component A and the liquid of component B in a mass ratio of 97:3; then apply the mixture on the surface of the floor after curing, with the amount of the mixture used being 10~20g / m2; (3) Continue drying at room temperature for 8 hours to form a hardened material layer on the surface of the floor, and finally obtain a cement-based floor with a hardened material layer.

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