A frost-resistant anti-permeation coating based on fluorosilane modified epoxy resin and a preparation method thereof

Abstract

The application belongs to the technical field of concrete protection, and particularly relates to an anti-freezing and anti-seepage coating based on fluorosilane modified epoxy resin and a preparation method thereof. The anti-freezing and anti-seepage coating based on fluorosilane modified epoxy resin comprises 30-40 parts of fluorosilane modified epoxy resin, 30-60 parts of a curing agent, 0.5-1.5 parts of a curing accelerator, and 1-2.5 parts of a wetting agent. The fluorosilane modified epoxy resin is synthesized by grafting reaction of fluoroalkane, silane and epoxy compound. The epoxy compound is composed of bisphenol A type epoxy resin and multi-functional glycidyl ether resin. The curing agent comprises a polyamine curing agent and a polysulfide rubber curing agent. The anti-freezing and anti-seepage coating based on fluorosilane modified epoxy resin can form a hydrophobic low surface energy structure on the surface of concrete, and inhibit the penetration of corrosion ions and aqueous solution into the interior of concrete. Meanwhile, the coating based on fluorosilane modified resin has good permeability and water vapor permeability, and can endow the coating with excellent freeze-thaw resistance and effectively enhance the service life of concrete engineering.

Description

Technical Field

[0001] This invention belongs to the field of concrete protection technology, specifically relating to an antifreeze and anti-seepage coating based on fluorosilane-modified epoxy resin and its preparation method. Background Technology

[0002] Concrete possesses advantages such as good structural stability, durability, and economy, meeting diverse engineering needs and playing a vital role in modern building and infrastructure construction. However, in the complex climate of cold regions, the coupled effects of freeze-thaw cycles, salt erosion, and alternating wet and dry conditions lead to significant deterioration of the mechanical properties of concrete. Under freeze-thaw cycles, concrete develops internal and external cracks, resulting in a decrease in structural strength and stiffness, and even causing steel reinforcement corrosion. Freeze-thaw cycles reduce the basic mechanical and deformation properties of concrete, such as compressive strength, tensile strength, modulus of elasticity, and deformation characteristics, thereby reducing the serviceability and load-bearing capacity of concrete structures and significantly impacting the durability of hydraulic concrete in cold regions.

[0003] Inhibiting water penetration into concrete is an effective way to enhance its frost resistance and cold resistance. Applying organic coatings, such as epoxy, acrylic, chlorinated rubber, and polyurethane coatings, to the concrete surface forms a dense protective film that prevents water penetration and diffusion into the concrete pores, achieving waterproofing and frost resistance. Traditional organic coatings achieve waterproofing by sealing concrete pores, but they are difficult to achieve hydrophobicity, failing to meet the requirements of concrete projects in cold regions to resist frost damage. Fluorosilanes and silanes have low surface energy, and fluorosilanes have good permeability in concrete, easily forming hydrophobic structures on the concrete surface and pore surfaces, greatly enhancing the water repellency of concrete. However, existing fluorosilane coatings have low adhesion to concrete surfaces and are prone to peeling off in harsh and complex environments, severely limiting the frost resistance and seepage prevention performance of concrete.

[0004] Therefore, there is an urgent need to develop concrete coatings with high adhesion and excellent antifreeze and anti-seepage properties to enable concrete to serve stably in cold and harsh environments. Summary of the Invention

[0005] Technical issues:

[0006] Because concrete undergoes freeze-thaw cycles at temperatures as low as -20°C, the resin molecular chains in fluorosilane coatings freeze, reducing the interfacial bonding between the coating and concrete. This leads to the coating peeling and detaching from the concrete surface, failing to achieve the desired freeze-thaw resistance. To address these challenges, this invention employs a resin molecular network design to enhance the adhesion of the concrete surface coating. By introducing components that strongly interact with the concrete into the coating, the adhesion is strengthened during freeze-thaw cycles, thus achieving the goal of freeze-thaw resistance and waterproofing of the concrete.

[0007] Technical solution:

[0008] One objective of this invention is to provide a frost-resistant and seepage-proof coating for concrete surfaces to solve the problem of frost damage in cold regions in current concrete engineering projects.

[0009] To achieve the above-mentioned objectives, the technical solution adopted by this invention is as follows:

[0010] An antifreeze and anti-seepage coating based on fluorosilane-modified epoxy resin and its preparation method are characterized in that the coating comprises the following raw materials in parts by weight: 30-40 parts of fluorosilane-modified epoxy resin, 30-60 parts of curing agent, 0.5-1.5 parts of curing accelerator, and 1-2.5 parts of wetting agent.

[0011] Furthermore, the fluorosilane-modified epoxy resin is composed of fluorosilanes and silanes and epoxy compounds, wherein the mass ratio of fluorosilanes to epoxy compounds is 1:3 to 1:10.

[0012] Furthermore, the fluoroalkane is one of perfluorooctyl sulfonamide and perfluorohexyl sulfonamide; the silane is one of aminopropyl double-terminated polydimethylsiloxane, 3-aminopropyltriethoxysilane, and aminopropyl isooctylcage silsesquioxane.

[0013] Furthermore, the epoxy compound is composed of bisphenol A type epoxy resin and polyfunctional glycidyl ether resin, wherein the mass ratio of bisphenol A type epoxy resin to polyfunctional glycidyl ether resin is 4:1-10:1.

[0014] Furthermore, the mass percentage of fluoroalkane in the fluoroalkane and silane-like substances is 20%-40%, with the remainder being silane.

[0015] Further, the bisphenol A type epoxy resin is any one of E51, E35, and E20; the multifunctional glycidyl ether resin is one of glycerol triglycidyl ether, trimethylolpropane triglycidyl ether, and polypropylene glycol diglycidyl ether.

[0016] Furthermore, the curing agent is one of triethylenetetramine, polyamide 650, and diaminodiphenylmethane.

[0017] Furthermore, the curing accelerator is one of aminophenol, methyldiethanolamine, and salicylic acid.

[0018] Furthermore, the wetting agent is one of octadecyleneamine acetate, aminopropylamine dioleate, or fatty acid ethylene oxide adduct.

[0019] Another object of the present invention is to provide a method for preparing an antifreeze and anti-seepage coating based on fluorosilane-modified epoxy resin, comprising the following steps:

[0020] (1) Mix bisphenol A type epoxy resin with polyfunctional glycidyl ether resin and mix under mechanical stirring (300-600 r / min) for 10-20 min to obtain epoxy compound;

[0021] (2) Mix the epoxy compound with fluoroalkane and silane evenly, and react at 60-90℃ for 5-10h to obtain fluorosilane modified epoxy resin.

[0022] (3) Mix the fluorosilane-modified epoxy resin, curing agent, curing agent accelerator and wetting agent evenly, let stand for 10-15 minutes to obtain an antifreeze and seepage-proof coating based on fluorosilane-modified epoxy resin.

[0023] Beneficial effects:

[0024] (1) The antifreeze and anti-seepage coating based on fluorosilane modified epoxy resin provided by the present invention introduces fluorosilane substances with low surface energy and high permeability into the resin network structure in a covalent manner through a polymer chemical modification method, thereby giving the coating excellent water-blocking and antifreeze properties and improving the service life of concrete.

[0025] (2) The antifreeze and seepage-proof coating based on fluorosilane modified epoxy resin provided by the present invention utilizes the interfacial interaction between the silane structure in the resin molecular chain and concrete to significantly enhance the adhesion of the coating; the construction method of the antifreeze and seepage-proof coating provided by the present invention is simple, has a wide range of applications, is easy to scale up, and has broad application prospects. Attached Figure Description

[0026] Figure 1 This is a schematic diagram of the molecular structure of the fluorosilane-modified epoxy resin in Example 1.

[0027] Figure 2 This is a test image showing the adhesion of the antifreeze and anti-seepage coating based on fluorosilane-modified epoxy resin to the concrete surface in Example 1. Detailed Implementation

[0028] The technical solution of the present invention will be further explained and described below with reference to the accompanying drawings and specific embodiments. It is worth noting that the following embodiments are only preferred embodiments of the present invention and should not be construed as limiting the present invention. The scope of protection of the present invention should be determined by the contents of the claims. Modifications and substitutions made by those skilled in the art to the technical solution of the present invention without creative effort all fall within the scope of protection of the present invention.

[0029] Example 1

[0030] (1) Mix 5g of E51 epoxy resin with 1g of glycerol triglycidyl ether and mix for 10min under mechanical stirring (300r / min) to obtain epoxy compound;

[0031] (2) 5g of epoxy compound was mixed evenly with 0.5g of perfluorooctyl sulfonamide and 0.5g of aminopropyl double-terminated polydimethylsiloxane, and reacted at 60℃ for 6h to obtain fluorosilane-modified epoxy resin. Figure 1 );

[0032] (3) Take 3 parts of fluorosilane-modified epoxy resin, 3 parts of polyamide 650, 0.5 parts of aminophenol and 1 part of aminopropylamine dioleate, mix them evenly, let stand for 10 minutes, and obtain an antifreeze and seepage-proof coating based on fluorosilane-modified epoxy resin.

[0033] Figure 2 The image shows the adhesion test results of the antifreeze and anti-seepage coating based on fluorosilane-modified epoxy resin on the concrete surface in this embodiment. It can be seen that the adhesion strength is as high as 8.07 MPa, indicating that the prepared antifreeze and anti-seepage coating has excellent adhesion performance on the concrete surface.

[0034] Example 2

[0035] (1) Mix 5g of E44 epoxy resin with 1g of polypropylene glycol diglycidyl ether and mix for 10min under mechanical stirring (300r / min) to obtain epoxy compound;

[0036] (2) Mix 5g of epoxy compound with 0.5g of perfluorooctyl sulfonamide and 0.5g of aminopropyl double-terminated polydimethylsiloxane evenly, and react at 60°C for 6h to obtain fluorosilane modified epoxy resin.

[0037] (3) Take 3 parts of fluorosilane-modified epoxy resin, 3 parts of polyamide 650, 0.5 parts of aminophenol and 1 part of aminopropylamine dioleate, mix them evenly, let stand for 10 minutes, and obtain an antifreeze and seepage-proof coating based on fluorosilane-modified epoxy resin.

[0038] Example 3

[0039] (1) Mix 5g of E51 epoxy resin with 1g of glycerol triglycidyl ether and mix for 10min under mechanical stirring (300r / min) to obtain epoxy compound;

[0040] (2) Mix 5g of epoxy compound with 0.5g of perfluorooctyl sulfonamide and 0.5g of aminopropyl isooctyl cage silsesquioxane evenly, and react at 60°C for 6h to obtain fluorosilane modified epoxy resin.

[0041] (3) Take 3 parts of fluorosilane-modified epoxy resin, 3 parts of polyamide 650, 0.5 parts of aminophenol and 1 part of aminopropylamine dioleate, mix them evenly, let stand for 15 minutes, and obtain an antifreeze and anti-seepage coating based on fluorosilane-modified epoxy resin.

[0042] Example 4

[0043] (1) Mix 5g of E51 epoxy resin with 1g of trimethylolpropane triglycidyl ether and mix for 12min under mechanical stirring (300r / min) to obtain epoxy compound;

[0044] (2) Mix 5g of epoxy compound with 0.5g of perfluorohexyl sulfonamide and 0.5g of aminopropyl isooctyl cage silsesquioxane evenly, and react at 60°C for 6h to obtain fluorosilane modified epoxy resin.

[0045] (3) Take 3 parts of fluorosilane-modified epoxy resin, 3 parts of diaminodiphenylmethane, 0.5 parts of aminophenol and 1 part of aminopropylamine dioleate, mix them evenly, let stand for 15 minutes, and obtain an antifreeze and anti-seepage coating based on fluorosilane-modified epoxy resin.

[0046] Comparative Example 1

[0047] (1) Mix 5g of E51 epoxy resin with 1g of glycerol triglycidyl ether and mix for 10min under mechanical stirring (300r / min) to obtain epoxy compound;

[0048] (2) Take 3 parts of epoxy compound, 3 parts of polyamide 650, 0.5 parts of aminophenol and 1 part of aminopropylamine dioleate, mix them evenly, let stand for 10 minutes, and obtain an antifreeze and anti-seepage coating based on fluorosilane modified epoxy resin.

[0049] Comparative Example 2

[0050] (1) Mix 5g of E51 epoxy resin with 1g of glycerol triglycidyl ether and mix for 10min under mechanical stirring (300r / min) to obtain epoxy compound;

[0051] (2) Mix 5g of epoxy compound with 0.5g of perfluorohexyl sulfonamide evenly and react at 60°C for 6h to obtain fluoroalkyl modified epoxy resin;

[0052] (2) Take 3 parts of fluorosilane-modified epoxy resin, 3 parts of polyamide 650, 0.5 parts of aminophenol and 1 part of aminopropylamine dioleate, mix them evenly, let stand for 10 minutes, and obtain an antifreeze and anti-seepage coating based on fluorosilane-modified epoxy resin.

[0053] Comparative Example 3

[0054] (1) Mix 5g of E51 epoxy resin with 1g of glycerol triglycidyl ether and mix for 10min under mechanical stirring (300r / min) to obtain epoxy compound;

[0055] (2) Mix 5g of epoxy compound with 0.5g of aminopropyl double-terminated polydimethylsiloxane until uniform and react at 60°C for 6h to obtain fluoroalkyl modified epoxy resin.

[0056] (2) Take 3 parts of silane-modified epoxy resin, 3 parts of polyamide 650, 0.5 parts of aminophenol and 1 part of aminopropylamine dioleate, mix them evenly, let stand for 10 minutes, and obtain an antifreeze and anti-seepage coating based on fluorosilane-modified epoxy resin.

Claims

1. A frost-resistant and seepage-proof coating based on fluorosilane-modified epoxy resin, characterized in that, The coating comprises the following raw materials in parts by weight: 30-40 parts of fluorosilane-modified epoxy resin, 30-60 parts of curing agent, 0.5-1.5 parts of curing accelerator, and 1-2.5 parts of wetting agent; the preparation method of the fluorosilane-modified epoxy resin includes: thoroughly mixing bisphenol A type epoxy resin and polyfunctional glycidyl ether resin to obtain an epoxy compound; uniformly mixing the epoxy compound with fluoroalkane and silane, and reacting at 60-90℃ for 5-10 hours to obtain fluorosilane-modified epoxy resin; the mass ratio of the fluoroalkane and silane substances to the epoxy compound is 1:3-1:10; The fluoroalkane and silane compounds contain 20%-40% fluoroalkane by mass, with the remainder being silane. The fluoroalkane is one of perfluorooctyl sulfonamide and perfluorohexyl sulfonamide; the silane is one of aminopropyl double-terminated polydimethylsiloxane, 3-aminopropyltriethoxysilane, and aminopropyl isooctyl cage-like silsesquioxane. The epoxy compound is composed of bisphenol A type epoxy resin and polyfunctional glycidyl ether resin, and the mass ratio of bisphenol A type epoxy resin to polyfunctional glycidyl ether resin is 4:1-10:

1.

2. The antifreeze and anti-seepage coating based on fluorosilane-modified epoxy resin as described in claim 1, characterized in that, The bisphenol A type epoxy resin is any one of E44, E35, and E20; the multifunctional glycidyl ether resin is one of glycerol triglycidyl ether, trimethylolpropane triglycidyl ether, and polypropylene glycol diglycidyl ether.

3. The antifreeze and anti-seepage coating based on fluorosilane-modified epoxy resin as described in claim 1, characterized in that, The curing agent is one of triethylenetetramine, polyamide 650, and diaminodiphenylmethane.

4. The antifreeze and anti-seepage coating based on fluorosilane-modified epoxy resin as described in claim 1, characterized in that, The curing accelerator is one of aminophenol, methyldiethanolamine, and salicylic acid.

5. The antifreeze and anti-seepage coating based on fluorosilane-modified epoxy resin as described in claim 1, characterized in that, The wetting agent is one of octadeceneamine acetate, aminopropylamine dioleate, or fatty acid ethylene oxide adduct.

6. A method for preparing an antifreeze and anti-seepage coating based on fluorosilane-modified epoxy resin as described in any one of claims 1-5, characterized in that, Includes the following steps: (1) Bisphenol A type epoxy resin and polyfunctional glycidyl ether resin are thoroughly mixed to obtain an epoxy compound; (2) Mix the epoxy compound with fluoroalkyl and silane evenly and react at 60-90℃ for 5-10h to obtain fluorosilane modified epoxy resin. (3) Mix the fluorosilane-modified epoxy resin, curing agent, curing agent accelerator and wetting agent evenly, let stand for 10-15 minutes to obtain the antifreeze and seepage-proof coating.

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