A high-permeability sprayed material, a preparation method and application thereof

Abstract

This invention proposes a high-penetration spray coating material, its preparation method, and its application, belonging to the field of coating technology. It includes component A and component B. Component A is prepared from the following raw materials in parts by weight: 10-15 parts polyurethane prepolymer, 5-7 parts nano-curing agent, 1-2 parts triethanolamine, and 20-25 parts acetone. Component B is prepared from the following raw materials in parts by weight: 70-100 parts epoxy resin, 1.5-2.5 parts toughening agent, 1-2 parts accelerator, and 14-17 parts benzaldehyde. The high-penetration spray coating material prepared by this invention is a high-performance, high-durability, and high-penetration waterproof spray coating material with good weather resistance, durability, excellent mechanical properties, good flame retardancy, high bonding strength with concrete, good pourability, and fast curing speed, showing broad application prospects.

Description

Technical Field

[0001] This invention relates to the field of coating technology, specifically to a high-penetration spraying material, its preparation method, and its application. Background Technology

[0002] Traditional waterproofing materials, such as emulsified asphalt and polyurethane, form a waterproof film on the surface of concrete structures, providing good waterproofing. However, due to stress, this waterproof film is easily damaged, leaving the concrete structure vulnerable to corrosion again. Therefore, high-performance, high-durability, and high-permeability waterproofing materials will be the future market trend.

[0003] Chinese patent document CN102504670A discloses a penetrating epoxy resin waterproof coating for concrete, comprising two components, A and B, with a weight percentage ratio of A:B = 5-15:1. Component A contains 20%-70% epoxy resin, 10%-50% reactive diluent, and 10%-40% epoxy reactive modifier; component B contains 10%-90% curing agent, 1%-20% accelerator, and 1%-10% penetration enhancer. This patent uses polyamines and / or low-molecular-weight polyamides as epoxy resin curing agents. The curing agents have high viscosity and require significant solvent dilution to reduce viscosity and increase penetration. However, epoxy resins using this series of curing agents exhibit unstable penetration performance. While initial penetration is good during application, defects such as low strength and easy delamination easily occur after solvent evaporation. Meanwhile, the curing agent and epoxy resin have poor toughness after curing. If the product's flexibility is adjusted by adding toughening agents, once the performance of the toughening agents deviates or is added inappropriately, the product will be prone to aging and brittle rebound after curing, which will lead to damage to the waterproof layer. Summary of the Invention

[0004] The purpose of this invention is to propose a high-penetration spraying material, its preparation method, and its application. This spraying material is a high-performance, high-durability, and high-penetration waterproof spraying material with good weather resistance, durability, excellent mechanical properties, good flame retardancy, high bonding strength with concrete, good groutability, and fast curing speed, and has broad application prospects.

[0005] The technical solution of this invention is implemented as follows:

[0006] This invention provides a high-penetration spraying material, comprising component A and component B. Component A is prepared from the following raw materials in parts by weight: 10-15 parts of polyurethane prepolymer, 5-7 parts of nano-curing agent, 1-2 parts of triethanolamine, and 20-25 parts of acetone. Component B is prepared from the following raw materials in parts by weight: 70-100 parts of epoxy resin, 1.5-2.5 parts of toughening agent, 1-2 parts of accelerator, and 14-17 parts of benzaldehyde.

[0007] As a further improvement of the present invention, the polyurethane prepolymer is prepared as follows: polyethylene glycol and toluene diisocyanate are mixed, heated and stirred to react, and then an amino-containing silane coupling agent is added and stirred to react to obtain the polyurethane prepolymer.

[0008] As a further improvement of the present invention, in the polyethylene glycol and toluene diisocyanate, OH - and NCO - The molar ratio is 0.8-1.0:1, the polyethylene glycol is polyethylene glycol 200 or polyethylene glycol 400, the mass ratio of polyethylene glycol to amino-containing silane coupling agent is 10:1-2, the heating and stirring reaction temperature is 75-85℃, the time is 0.5-1.5h, the amino-containing silane coupling agent is selected from at least one of KH550, KH602, and KH792, and the stirring reaction time is 1-2h.

[0009] As a further improvement of the present invention, the preparation method of the nano-curing agent is as follows:

[0010] S1. Preparation of polydopamine-modified nano-titanium oxide particles: Tetrabutyl titanate was dissolved in ethanol, glacial acetic acid and water were added, the mixture was stirred and reacted, centrifuged, washed and dried, the product was added to water, the pH of the solution was adjusted with Tris-HCl solution and NaOH, dopamine hydrochloride was added, the mixture was heated and stirred and reacted, centrifuged, washed and dried to obtain polydopamine-modified nano-titanium oxide particles.

[0011] S2. Preparation of aldehyde-containing flame retardant: 5-hydroxyfurfural, triethylamine, and phosphorus oxychloride are reacted by heating and stirring in a solvent to prepare an aldehyde-containing flame retardant with the structure shown in Formula I:

[0012]

[0013] S3. Preparation of nano-curing agent: The aldehyde-containing flame retardant and polydopamine-modified nano-titanium oxide particles are mixed and added to water, heated and stirred to react, centrifuged, washed and dried to obtain nano-curing agent.

[0014] As a further improvement of the present invention, the mass ratio of tetrabutyl titanate, glacial acetic acid, and dopamine hydrochloride in step S1 is 15-20:3-5:10-12, the stirring reaction time is 2-4 hours, the pH value of the solution is adjusted to 8.5-9.5, the heating and stirring reaction temperature is 45-55°C, and the time is 1-3 hours.

[0015] As a further improvement of the present invention, the molar ratio of 5-hydroxyfurfural, triethylamine and phosphorus oxychloride in step S2 is 3-3.1:4-6:1, the solvent is at least one of acetonitrile, chloroform, ethyl acetate, petroleum ether and tetrahydrofuran, and the heating and stirring reaction temperature is 40-50°C and the time is 3-6 h.

[0016] As a further improvement of the present invention, the mass ratio of the aldehyde-containing flame retardant and the polydopamine-modified nano-titanium oxide particles in step S3 is 1-2:10, and the heating and stirring reaction temperature is 60-70℃, and the time is 1-2h.

[0017] As a further improvement of the present invention, the epoxy resin is epoxy resin E-44 or epoxy resin E-51, the accelerator is K54 or DMP-30, and the toughening agent is at least one of LD-410, GK-D410 or GK-D411.

[0018] This invention further protects a method for preparing the above-mentioned high-penetration spray coating material, comprising the following steps:

[0019] (1) Mix polyurethane prepolymer, nano-curing agent, triethanolamine and acetone evenly to obtain component A;

[0020] (2) Mix epoxy resin, toughening agent, accelerator and benzaldehyde evenly to obtain component B;

[0021] (3) Component A and Component B are mixed and sprayed out in the spray gun of the spraying equipment, and react and solidify into a high-penetration spraying material.

[0022] This invention further protects the application of the above-mentioned high-penetration spraying material in the preparation of waterproof building materials.

[0023] The present invention has the following beneficial effects:

[0024] The high-penetration spraying material of this invention comprises a blend of a component A with a low molecular weight and a component B with a high molecular weight. It is applied using a simple spraying machine. After the spraying is completed, the low molecular weight substance penetrates into the concrete and solidifies, filling the micropores in the concrete; the high molecular weight substance remains on the concrete wall, forming a waterproof coating.

[0025] In component A of this invention, the polyurethane prepolymer has a low molecular weight and can form an interpenetrating network with the subsequent epoxy resin, enhancing the toughness of the epoxy resin. At the same time, the prepolymer also incorporates an amino-containing silane coupling agent, whose amino groups can react with the subsequent epoxy resin, accelerating the curing of the epoxy resin, shortening the curing time, and achieving rapid curing at room temperature.

[0026] The A component of this invention also contains a nano-curing agent, with nano-titanium dioxide particles prepared by sol-gel reaction as the core. The surface is modified with polydopamine and has abundant amino groups. Some of these amino groups can react with aldehyde-containing flame retardants, while others can undergo ring-opening curing reactions with epoxy resin, thus acting as a curing agent. At the same time, it can also introduce flame retardant components into the epoxy resin molecular chain, improving the flame retardancy of the epoxy resin. Furthermore, the titanium dioxide can be uniformly introduced into the epoxy resin molecular chain, improving the mechanical properties, antibacterial properties, and photocatalytic degradation of VOCs of the coating, thus enhancing its environmental friendliness. It also has good reflectivity to ultraviolet light, improving the weather resistance and durability of the coating.

[0027] This invention allows acetone and benzaldehyde to react to generate benzaldehyde-1-methyl ...

[0028] The high-penetration spraying material prepared by this invention is a high-performance, high-durability and high-penetration spraying waterproof material. It has good weather resistance, durability, excellent mechanical properties, good flame retardancy, high bonding strength with concrete, good groutability, and fast curing speed, and has broad application prospects. Detailed Implementation

[0029] The technical solutions in the embodiments of the present invention will be clearly and completely described below. Obviously, the described embodiments are only some embodiments of the present invention, and not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of the present invention.

[0030] Preparation Example 1: Preparation of Polyurethane Prepolymer

[0031] The method is as follows: Mix 10g of polyethylene glycol 200 and toluene diisocyanate, wherein the polyethylene glycol 200 and toluene diisocyanate contain OH... - and NCO - The molar ratio of the two components was 0.8:1. The mixture was heated to 75°C and stirred for 0.5 hours. Then, 1 g of silane coupling agent KH550 was added, and the mixture was stirred at 45°C for 1 hour to obtain the polyurethane prepolymer.

[0032] Preparation Example 2: Preparation of Polyurethane Prepolymer

[0033] The method is as follows: Mix 10g of polyethylene glycol 400 and toluene diisocyanate, wherein the polyethylene glycol 400 and toluene diisocyanate contain OH... - The molar ratio of NCO- to NCO- is 1:1. The mixture is heated to 85°C and stirred for 1.5 hours. Then, 2g of silane coupling agent KH602 is added, and the mixture is stirred at 45°C for 2 hours to obtain a polyurethane prepolymer.

[0034] Preparation Example 3: Preparation of Polyurethane Prepolymer

[0035] The method is as follows: Mix 10g of polyethylene glycol 200 and toluene diisocyanate, wherein the polyethylene glycol 200 and toluene diisocyanate contain OH... - and NCO - The molar ratio of the two components was 0.9:1. The mixture was heated to 80°C and stirred for 1 hour. Then, 1.5 g of silane coupling agent KH792 was added, and the mixture was stirred at 45°C for 1.5 hours to obtain the polyurethane prepolymer.

[0036] Comparative Preparation Example 1

[0037] The difference compared to Preparation Example 3 is that the silane coupling agent KH792 was not added.

[0038] Preparation Example 4: Preparation of Nano-Curing Agent

[0039] The method is as follows:

[0040] S1. Preparation of polydopamine-modified nano-titanium oxide particles: 15g tetrabutyl titanate was dissolved in 200mL ethanol, 3g glacial acetic acid and 10mL water were added, the mixture was stirred and reacted for 2h, centrifuged, washed and dried, the product was added to water, the pH of the solution was adjusted to 8.5 with Tris-HCl solution and NaOH, 10g dopamine hydrochloride was added, the mixture was heated to 45℃, stirred and reacted for 1h, centrifuged, washed and dried to obtain polydopamine-modified nano-titanium oxide particles;

[0041] S2. Preparation of aldehyde-containing flame retardant: 0.03 mol 5-hydroxyfurfural, 0.04 mol triethylamine, and 0.01 mol phosphorus oxychloride were added to 200 mL acetonitrile, heated to 40 °C, and stirred for 3 h. The solvent was removed under reduced pressure, filtered, washed, and dried to obtain the aldehyde-containing flame retardant; ESI-MS calculated value: C 15 H 10 O 10 P(M+H) + 380.99, measured value: 381.0, yield: 85%.

[0042] MRI results: 1H NMR (300MHz, CDCl3) δ9.56 (s, 3H), 7.21 (d, J=5.5Hz, 3H), 6.67 (d, J=5.4Hz, 3H).

[0043] S3. Preparation of nano-curing agent: 1g of aldehyde-containing flame retardant and 10g of polydopamine-modified nano-titanium oxide particles were mixed and added to 100mL of water, heated to 60℃, stirred and reacted for 1h, centrifuged, washed and dried to obtain nano-curing agent.

[0044] Preparation Example 5: Preparation of Nano-Curing Agent

[0045] The method is as follows:

[0046] S1. Preparation of polydopamine-modified nano-titanium oxide particles: 20g tetrabutyl titanate was dissolved in 200mL ethanol, 5g glacial acetic acid and 10mL water were added, the mixture was stirred and reacted for 4h, centrifuged, washed and dried, the product was added to water, the pH of the solution was adjusted to 9.5 with Tris-HCl solution and NaOH, 12g dopamine hydrochloride was added, the mixture was heated to 55℃, stirred and reacted for 3h, centrifuged, washed and dried to obtain polydopamine-modified nano-titanium oxide particles;

[0047] S2. Preparation of aldehyde-containing flame retardant: 0.31 mol 5-hydroxyfurfural, 0.06 mol triethylamine and 0.01 mol phosphorus oxychloride were added to 200 mL acetonitrile, heated to 50 °C, stirred for 6 h, the solvent was removed under reduced pressure, filtered, washed and dried to obtain aldehyde-containing flame retardant;

[0048] S3. Preparation of nano-curing agent: 2g of aldehyde-containing flame retardant and 10g of polydopamine-modified nano-titanium oxide particles were mixed and added to 100mL of water, heated to 70℃, stirred and reacted for 2h, centrifuged, washed and dried to obtain nano-curing agent.

[0049] Preparation Example 6: Preparation of Nano Curing Agent

[0050] The method is as follows:

[0051] S1. Preparation of polydopamine-modified nano-titanium oxide particles: 17g tetrabutyl titanate was dissolved in 200mL ethanol, 4g glacial acetic acid and 10mL water were added, the mixture was stirred for 3h, centrifuged, washed and dried, the product was added to water, the pH of the solution was adjusted to 9 with Tris-HCl solution and NaOH, 11g dopamine hydrochloride was added, the mixture was heated to 50℃, stirred for 2h, centrifuged, washed and dried to obtain polydopamine-modified nano-titanium oxide particles;

[0052] S2. Preparation of aldehyde-containing flame retardant: 0.0305 mol 5-hydroxyfurfural, 0.05 mol triethylamine and 0.01 mol phosphorus oxychloride were added to 200 mL acetonitrile, heated to 45 °C, stirred and reacted for 4.5 h, the solvent was removed under reduced pressure, filtered, washed and dried to obtain aldehyde-containing flame retardant;

[0053] S3. Preparation of nano-curing agent: 1.5g of aldehyde-containing flame retardant and 10g of polydopamine-modified nano-titanium oxide particles were mixed and added to 100mL of water, heated to 65℃, stirred and reacted for 1.5h, centrifuged, washed and dried to obtain nano-curing agent.

[0054] Comparative Preparation Example 2

[0055] The difference from Preparation Example 3 is that polydopamine modification was not performed in step S1.

[0056] Comparative preparation example 3

[0057] The difference compared to Preparation Example 3 is that steps S2 and S3 were not performed.

[0058] Example 1

[0059] This embodiment provides a high-penetration spraying material, the preparation method of which includes the following steps:

[0060] (1) Mix 10g of the polyurethane prepolymer prepared in Preparation Example 1, 5g of the nano-curing agent prepared in Preparation Example 4, 1g of triethanolamine and 20g of acetone for 30min to obtain component A.

[0061] (2) Mix 70g of epoxy resin E-51, 1.5g of toughening agent GK-D410, 1g of accelerator K54 and 14g of benzaldehyde for 30min to obtain component B.

[0062] (3) Component A and Component B are mixed and sprayed out in the spray gun of the spraying equipment, and react and solidify into a high-penetration spraying material.

[0063] Example 2

[0064] This embodiment provides a high-penetration spraying material, the preparation method of which includes the following steps:

[0065] (1) Mix 15g of the polyurethane prepolymer prepared in Preparation Example 2, 7g of the nano-curing agent prepared in Preparation Example 5, 2g of triethanolamine and 25g of acetone for 30min to obtain component A.

[0066] (2) Mix 100g of epoxy resin E-44, 2.5g of toughening agent LD-410, 2g of accelerator K54 and 17g of benzaldehyde for 30min to obtain component B.

[0067] (3) Component A and Component B are mixed and sprayed out in the spray gun of the spraying equipment, and react and solidify into a high-penetration spraying material.

[0068] Example 3

[0069] This embodiment provides a high-penetration spraying material, the preparation method of which includes the following steps:

[0070] (1) 12g of the polyurethane prepolymer prepared in Preparation Example 3, 6g of the nano-curing agent prepared in Preparation Example 6, 1.5g of triethanolamine and 22g of acetone were stirred and mixed for 30min to obtain component A.

[0071] (2) Mix 85g of epoxy resin E-51, 2g of toughening agent LD-410, 1.5g of accelerator DMP-30 and 15g of benzaldehyde for 30 minutes to obtain component B.

[0072] (3) Component A and Component B are mixed and sprayed out in the spray gun of the spraying equipment, and react and solidify into a high-penetration spraying material.

[0073] Comparative Example 1

[0074] The difference from Example 3 is that the polyurethane prepolymer was prepared by Comparative Preparation Example 1.

[0075] Comparative Example 2

[0076] The difference from Example 3 is that the nano-curing agent was prepared from Comparative Preparation Example 2.

[0077] Comparative Example 3

[0078] The difference from Example 3 is that the nano-curing agent was prepared by Comparative Preparation Example 3.

[0079] Comparative Example 4

[0080] The difference compared to Example 3 is that no polyurethane prepolymer was added.

[0081] Comparative Example 5

[0082] The difference compared to Example 3 is that no nano-curing agent was added.

[0083] Test Example 1: Oxygen Index Test

[0084] The limiting oxygen index of the high-penetration spraying materials prepared in Examples 1-3 or Comparative Examples 1-5 was tested. The results are shown in Table 4.

[0085] Oxygen index test: Prepare rectangular strips of paint with dimensions of 150mm × 50mm, with 5 strips per group. Burn the strips in a flame for 3 minutes. The oxygen concentration at the point where the sample reaches 50mm from the top is the oxygen index of the sample.

[0086] Table 4

[0087] Example 1 35 Example 2 36 Example 3 36 Comparative Example 1 34 Comparative Example 2 30 Comparative Example 3 26 Comparative Example 4 33 Comparative Example 5 24

[0088] As can be seen from the table above, the high-penetration spray coating materials prepared in Examples 1-3 of the present invention have good flame retardant properties.

[0089] Test Example 2: Ultraviolet Shielding Performance

[0090] The high-penetration spray coatings prepared in Examples 1-3 or Comparative Examples 1-5 were tested for their UV shielding performance. The results are shown in Table 5.

[0091] The method in GB / T18830-2009 is adopted, using ultraviolet-visible diffuse reflectance for testing. The formula is as follows:

[0092]

[0093] In the formula: E(λ) is the solar spectral radiance, W / (m²). 2 ·nm); ε(λ) is the relative erythema effect value; T i (λ) represents the spectral transmittance of the sample at wavelength λ; Δλ represents the wavelength interval, in nm.

[0094] Table 5

[0095]

[0096]

[0097] As can be seen from the table above, the high-penetration spray coating materials prepared in Examples 1-3 of the present invention have good ultraviolet shielding performance.

[0098] Test Example 3

[0099] The high-penetration spraying materials prepared in Examples 1-3 and Comparative Examples 1-5 of this invention were subjected to comprehensive performance tests, and the results are shown in Table 3.

[0100] Table 3

[0101]

[0102] As can be seen from the table above, the high-penetration spraying materials prepared in Examples 1-3 of the present invention have good comprehensive performance.

[0103] The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention. Any modifications, equivalent substitutions, improvements, etc., made within the spirit and principles of the present invention should be included within the protection scope of the present invention.

Claims

1. A high-penetration spray coating material, characterized in that, The product comprises component A and component B. Component A is prepared from the following raw materials in parts by weight: 10-15 parts polyurethane prepolymer, 5-7 parts nano-curing agent, 1-2 parts triethanolamine, and 20-25 parts acetone. Component B is prepared from the following raw materials in parts by weight: 70-100 parts epoxy resin, 1.5-2.5 parts toughening agent, 1-2 parts accelerator, and 14-17 parts benzaldehyde. The polyurethane prepolymer is prepared as follows: polyethylene glycol and toluene diisocyanate are mixed, heated and stirred to react, then an amino-containing silane coupling agent is added, and the mixture is stirred to react, thus obtaining the polyurethane prepolymer. In the polyethylene glycol and toluene diisocyanate, OH... - and NCO - The molar ratio is 0.8-1.0:1, the polyethylene glycol is polyethylene glycol 200 or polyethylene glycol 400, the mass ratio of polyethylene glycol to amino-containing silane coupling agent is 10:1-2, the heating and stirring reaction temperature is 75-85℃, the time is 0.5-1.5h, the amino-containing silane coupling agent is selected from at least one of KH550, KH602, and KH792, and the stirring reaction time is 1-2h; the preparation method of the nano-curing agent is as follows: S1. Preparation of polydopamine modified nano-titanium oxide particles: dissolve tetrabutyl titanate in ethanol, add glacial acetic acid and water, stir the reaction, centrifuge, wash, dry, add the product to water, adjust the pH value of the solution with Tris-HCl solution and NaOH, add dopamine hydrochloride, heat and stir the reaction, centrifuge, wash, dry, to obtain polydopamine modified nano-titanium oxide particles; S2. Preparation of aldehyde-containing flame retardants: 5-hydroxyfurfural, triethylamine, and phosphorus oxychloride are reacted by heating and stirring in a solvent to prepare an aldehyde-containing flame retardant with the structure shown in Formula I: Formula I; S3. Preparation of nano-curing agent: An aldehyde-containing flame retardant and polydopamine-modified nano-titanium oxide particles are mixed and added to water, heated and stirred to react, centrifuged, washed, and dried to obtain the nano-curing agent; the mass ratio of tetrabutyl titanate, glacial acetic acid, and dopamine hydrochloride in step S1 is 15-20:3-5:10-12, the stirring reaction time is 2-4 hours, the pH of the solution is adjusted to 8.5-9.5, the heating and stirring reaction temperature is 45-55℃, and the time is 1-3 hours. h; In step S2, the molar ratio of 5-hydroxyfurfural, triethylamine, and phosphorus oxychloride is 3-3.1:4-6:1, the solvent is at least one of acetonitrile, chloroform, ethyl acetate, petroleum ether, and tetrahydrofuran, and the heating and stirring reaction temperature is 40-50℃ for 3-6 h; In step S3, the mass ratio of the aldehyde-containing flame retardant and polydopamine-modified nano-titanium oxide particles is 1-2:10, and the heating and stirring reaction temperature is 60-70℃ for 1-2 h.

2. The high-penetration spraying material according to claim 1, characterized in that, The epoxy resin is epoxy resin E-44 or epoxy resin E-51, the accelerator is K54 or DMP-30, and the toughening agent is at least one of LD-410, GK-D410, or GK-D411.

3. A method for preparing a high-penetration spraying material as described in claim 1 or 2, characterized in that, The process includes the following steps: (1) mixing polyurethane prepolymer, nano-curing agent, triethanolamine and acetone evenly to obtain component A; (2) mixing epoxy resin, toughening agent, accelerator and benzaldehyde evenly to obtain component B; (3) mixing component A and component B in the spray gun of the spraying equipment and spraying them out to react and solidify into a high-penetration spraying material.

4. The application of a high-penetration spraying material as described in claim 1 or 2 in the preparation of waterproof building materials.

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