A water-based super-hydrophobic consolidating material for TIT embedded sealing layer

Abstract

The present invention discloses a water-based super-hydrophobic consolidating material for a TIT embedded sealing layer, comprising: a water-based fluorine-containing silicon epoxy curing agent, a fluorine-containing silicon epoxy resin emulsion, a leveling agent, a defoaming agent and a micro-nano particle modified slurry. After the water-based super-hydrophobic consolidating material for the embedded sealing layer is cured, the contact angle is greater than 150°, the hardness is greater than 4H, the artificial aging time is greater than 1500h, the pull-out strength is greater than 2MPa, and the pendulum friction value is greater than 70. Compared with the solvent-based consolidating material currently used in the market, the water-based super-hydrophobic consolidating material for the TIT embedded sealing layer of the present invention is non-toxic, non-flammable, safe to use, does not pollute the environment, and has the advantages of high adhesion, wear resistance, and aging resistance.

Description

Technical Field

[0001] The invention belongs to the field of polymer materials, and in particular relates to a water-based super-hydrophobic consolidating material for a TIT embedding sealing layer for roads. Background Art

[0002] TIT is the abbreviation of Thermosetting Inserting Technology. TIT anti-skid surface treatment technology mainly uses high-performance nano-grade thermosetting special materials as the core raw materials, and then combines a certain proportion of emulsified asphalt and a certain grade of wear-resistant fine aggregate to fill cracks, potholes and other defects on aging roads. After the water-based epoxy binder penetrates into the gaps in the road surface, a cross-linking reaction occurs, and it is embedded and integrated with the original road surface, so that the anti-skid aggregate "takes root" in the original road surface.

[0003] Waterborne epoxy resin not only has the advantages of general solvent-based epoxy resin, but also has many advantages such as low VOC content, no irritating taste, no harm to the human body, simple use, water washable, no pollution, etc., and has excellent properties such as good stability, high solid content, low viscosity, strong bonding performance, etc. However, due to the poor aging resistance, anti-icing and wear resistance of waterborne epoxy resin, its own performance defects lead to undesirable phenomena such as easy discoloration, shedding, peeling, and poor anti-icing effect of TIT embedded sealing layer, which limits the application of waterborne epoxy resin as a consolidating material in TIT embedded sealing layer.

[0004] The invention patent with application number 2015104076108 reports a super-hydrophobic anti-icing composite cement pavement structure and its preparation method. The pavement structure consists of an anti-icing functional layer and a main concrete layer. The anti-icing functional layer is a fiber concrete layer modified by a modified hydrophobic agent, which has a super-hydrophobic anti-icing function. The modified hydrophobic agent is prepared from a hydrophobic emulsion material and a modified admixture, the dispersion medium of the hydrophobic emulsion material is a polyvinyl alcohol solution, and the dispersed phase is one or two of polymethylsiloxane and polydimethylhydrogensiloxane. The modified admixture is prepared by mixing nanoparticles and mildew inhibitors; the main concrete pavement layer is ordinary cement concrete. The pavement structure is prepared by a layered construction method. After pouring fiber concrete on the main concrete pavement layer, a modified hydrophobic agent is sprayed on its surface. The micro-nano secondary structure is constructed by the nanoparticles in the fibers exposed on the road surface and the hydrophobic agent, so that the pavement has a super-hydrophobic anti-icing function. However, due to the lack of cross-linking and the fact that it only relies on polysiloxane for hydrophobicity, its inherent performance defects lead to undesirable phenomena such as easy shedding, peeling, and poor anti-icing effect of the hydrophobic coating. Therefore, it is urgent to develop a water-based super-hydrophobic consolidating material for high-performance TIT embedded sealing layer. Summary of the invention

[0005] The purpose of the present invention is to provide a water-based super-hydrophobic consolidating material for a TIT embedded sealing layer in order to solve the problems of easy shedding, peeling and poor anti-icing effect of hydrophobic coatings applied on existing pavements.

[0006] In order to achieve the above-mentioned purpose, the present invention adopts the following technical scheme: a water-based super-hydrophobic consolidating material for a TIT embedded sealing layer, comprising: a water-based fluorine-containing silicon epoxy curing agent, a fluorine-containing silicon epoxy resin emulsion, a leveling agent, a defoaming agent and a micro-nano particle modified slurry. After the water-based super-hydrophobic consolidating material for the embedded sealing layer is cured, the contact angle is greater than 150°, the hardness is greater than 4H, the artificial aging time is greater than 1500h, the pull-out strength is greater than 2MPa, and the pendulum friction value is ≥70.

[0007] Furthermore, the mass ratio of the water-based fluorinated silicon epoxy curing agent, the fluorinated silicon epoxy resin emulsion, the leveling agent, the defoaming agent and the micro-nano particle modified slurry is (80-100):100:(0.2-0.5):(0.3-1.0):(20-50).

[0008] Furthermore, the water-based fluorinated silicon epoxy curing agent is prepared by the following method:

[0009] (1) 50 to 80 parts by weight of fluorinated epoxy resin and 20 to 50 parts by weight of liquid fluorosilicone resin are placed in a stirred reactor and stirred evenly;

[0010] (2) adding a mixed solution of fluorinated epoxy resin and liquid fluorosilicone resin to a fluorinated low molecular weight polyamine at 85 to 95° C. within 1 to 3 hours, and reacting at 90 to 95° C. for 2 to 4 hours, wherein the molar ratio of epoxy groups of the fluorinated epoxy resin to the fluorinated low molecular weight polyamine is 1:0.8 to 1.2;

[0011] (3) adding a silicon-containing glycidyl ether capping agent dropwise to the mixed solution of (2) within 1 to 2 hours, and continuing the reaction at a temperature of 3 to 5 hours, wherein the ratio of the silicon-containing glycidyl ether capping agent to the fluorine-containing low molecular weight polyamine substance is 1:0.8 to 1.2;

[0012] (4) The mixed solution of (3) is cooled to room temperature, an acidic neutralizer is added, and the ratio of the neutralizer to the fluorine-containing low molecular weight polyamine substance is 1:0.4-0.8, and finally 60-100 parts by weight of deionized water is added to dilute it to prepare a water-based fluorine-containing silicon epoxy curing agent.

[0013] Furthermore, the fluorinated epoxy resin is diphenol hexafluoropropane diglycidyl ether, 1,4-bis(hydroxyhexafluoroisopropyl)benzene diglycidyl ether or 4,4'-dihydroxyoctafluorobiphenyl diglycidyl ether; the liquid fluorosilicone resin has a viscosity of 50 to 200 mPa·s; the silicon-containing glycidyl ether capping agent is a glycidyl ether containing silicon element, preferably tert-butyl dimethylsilyl glycidyl ether; the acidic neutralizer is a low molecular weight organic acid, preferably glacial acetic acid.

[0014] Furthermore, the fluorine-containing low molecular weight polyamine is a fluorine-containing diamine, preferably 2,2-bis[4-(4-aminophenoxy)phenyl]hexafluoropropane.

[0015] Furthermore, the fluorine-containing silicone epoxy resin emulsion is prepared by the following method: 70 to 90 parts by mass of fluorinated epoxy resin and 10 to 30 parts by mass of liquid fluorine silicone resin are put into a stirred reactor, the temperature is raised to 70 to 90° C., 10 to 20 parts by mass of carboxyl functional monomers, 1 to 3 parts by mass of antioxidants, 1 to 3 parts by mass of anti-ultraviolet agents, and 1 to 5 parts by mass of initiators are added, the reaction is carried out for 3 to 5 hours, the mixture is cooled to room temperature, an alkaline neutralizer in an amount equal to that of the carboxyl functional monomer and other substances is added, and then 80 to 120 parts by mass of deionized water are added under high-speed stirring, and the phases are inverted to obtain a uniform white liquid, thereby obtaining the fluorine-containing silicone epoxy resin emulsion.

[0016] Further, the fluorinated epoxy resin is diphenol hexafluoropropane diglycidyl ether, 1,4-bis(hydroxyhexafluoroisopropyl)benzene diglycidyl ether or 4,4'-dihydroxyoctafluorobiphenyl diglycidyl ether; the liquid fluorosilicone resin has a viscosity of 50 to 200 mPa·s; the carboxyl functional monomer is methacryloyloxyethyl maleic acid monoester, methacryloyloxyethyl phthalic acid monoester or methacryloyloxyethyl hexahydrophthalic acid monoester; the antioxidant is tetrakis[β-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate] pentaerythritol ester, β-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate, 1,1,3-tris(2-methyl-4-hydroxy-5-tert-butylphenyl)butane, 2,6-di-tert-butyl-4-methyl The invention relates to a novel nanostructured carbonyl cyanoacrylate (N-C-butyl cyanoacrylate) ...

[0017] Furthermore, the leveling agent is one of polyorganosiloxane, polyether-modified polyorganosiloxane or fluorine-containing surfactant, and the defoaming agent is an aqueous defoaming agent.

[0018] Furthermore, the micro-nanoparticle modified slurry is prepared by the following method: 5 parts by mass of micro-nanoparticles, 50 parts by mass of deionized water and a mixed solution of 0.5 to 1.5 parts by mass of a fluorine-containing silane coupling agent are added to a four-necked flask equipped with a stirring device, a thermometer and a condenser, heated to 105° C., and refluxed for 12 to 24 hours; after cooling to room temperature, the product is transferred to a rotary evaporator, and the deionized water is removed by heating and distillation; silicon-containing glycidyl ether is added, and ultrasonic dispersion is performed for 1 to 2 hours to obtain a micro-nanoparticle modified slurry with a solid content of 15% to 30%.

[0019] Furthermore, the micro-nano particles are micro-nano titanium dioxide, micro-nano silicon dioxide or micro-nano kaolin; the fluorine-containing silane coupling agent is heptadecafluorodecyltrimethoxysilane or tridecafluorooctyltriethoxysilane; and the silicon-containing glycidyl ether is preferably tert-butyldimethylsilyl glycidyl ether.

[0020] The beneficial effects of the present invention are as follows: (1) Compared with the solvent-based consolidating materials currently used in the market, the water-based super-hydrophobic consolidating materials for the TIT embedded sealing layer of the present invention have the advantages of being non-toxic, non-flammable, safe to use, and not polluting the environment. (2) Compared with the water-based super-hydrophobic consolidating materials currently used in the market, the water-based super-hydrophobic consolidating materials for the TIT embedded sealing layer of the present invention have the advantages of high adhesion, wear resistance, and aging resistance. (3) The present invention comprehensively considers the requirements for the use of water-based super-hydrophobic consolidating materials for TIT embedded sealing layers for pavement substrates, and obtains a self-emulsifying fluorinated epoxy resin emulsion by modifying the fluorinated epoxy resin with acrylic acid. There is no need to add a surfactant that reduces the water resistance and mechanical properties of the film after the consolidating material is cured; and a leveling agent and a water-based defoaming agent are added to improve the workability and stability of the water-based super-hydrophobic consolidating material; by using fluorinated epoxy resin, liquid fluorosilicone resin, fluorinated low molecular weight polyamine, silicon-containing glycidyl ether, and micro-nano The introduction of particle / fluorinated silane coupling agent modified slurry reduces the surface energy of the paint film after curing; under the action of micro-nanoparticles modified by fluorinated silane coupling agent, the coating presents a lotus leaf-like papillary structure, making the coating achieve a super-hydrophobic effect; through the curing action of water-based fluorinated silicon epoxy curing agent and fluorinated silicon epoxy resin emulsion, the cross-linking degree of the coating is improved, and the adhesion, wear resistance and aging resistance of the cured coating are further improved, so that the water-based super-hydrophobic consolidating material used in the TIT embedded sealing layer can meet the use requirements under different conditions. BRIEF DESCRIPTION OF THE DRAWINGS

[0021] Figure 1 It is a schematic diagram of sandpaper friction of the super-hydrophobic layer of the super-hydrophobic consolidating material prepared in Example 1 coated on a concrete pavement after solidification under the weight of a 300g or 1000g weight.

[0022] Figure 2This is a contact angle test result diagram of the super hydrophobic consolidation material prepared in Example 1 after 0 to 100 cycles of friction under the action of 300g weight gravity.

[0023] Figure 3 The contact angle and deicing force of the super-hydrophobic consolidating material prepared in Example 1 after the sample is rubbed for 0 to 50 cycles under the action of a 1000 g weight. Specific implementation methods

[0024] In order to enable those skilled in the art to better understand the solution of the present application, the technical solution in the embodiments of the present application will be clearly and completely described below in conjunction with the drawings in the embodiments of the present application. Obviously, the described embodiments are only part of the embodiments of the present application, not all of the embodiments. Based on the embodiments in the present application, all other embodiments obtained by ordinary technicians in this field without creative work should fall within the scope of protection of the present application.

[0025] It should be noted that the terms "including" and "having" and any variations thereof in the specification and claims of the present application and the above-mentioned drawings are intended to cover non-exclusive inclusions. For example, a process, method, system, product or apparatus comprising a series of steps or units is not necessarily limited to those steps or units clearly listed, but may include other steps or units that are not clearly listed or inherent to these processes, methods, products or apparatuses.

[0026] A water-based super-hydrophobic consolidating material for a TIT embedded sealing layer, the water-based super-hydrophobic consolidating material comprising: a water-based fluorine-containing silicon epoxy curing agent, a fluorine-containing silicon epoxy resin emulsion, a leveling agent, a defoaming agent and a micro-nano particle modified slurry. After the water-based super-hydrophobic consolidating material for the embedded sealing layer is cured, the contact angle is greater than 150°, the hardness is greater than 4H, the artificial aging is greater than 1500h, the pull-out strength is greater than 2MPa, and the pendulum friction value is ≥70.

[0027] The leveling agent is one of polyorganosiloxane, polyether-modified polyorganosiloxane or fluorine-containing surfactant.

[0028] The defoamer is a water-based defoamer.

[0029] The method for preparing a TIT embedded sealing layer using an aqueous super-hydrophobic consolidating material comprises the following steps:

[0030] (1) Preparation of fluorinated silicone epoxy resin emulsion

[0031] 70-90 parts by weight of fluorinated epoxy resin and 10-30 parts by weight of liquid fluorosilicone resin are put into a stirred reactor, the temperature is raised to 70-90° C., 10-20 parts by weight of carboxyl functional monomer, 1-3 parts by weight of antioxidant, 1-3 parts by weight of anti-ultraviolet agent and 1-5 parts by weight of initiator are added, the reaction is carried out for 3-5 hours, the mixture is cooled to room temperature, an alkaline neutralizer in an amount equal to that of the carboxyl functional monomer and other substances is added, and then 80-120 parts by weight of deionized water are added under high-speed stirring, and the phases are inverted to obtain a uniform white liquid, thereby preparing a fluorine-containing silicone epoxy resin emulsion.

[0032] (2) Preparation of water-based fluorinated silicon epoxy curing agent

[0033] 50-80 parts by weight of fluorinated epoxy resin and 20-50 parts by weight of liquid fluorosilicone resin are put into a stirred reactor and stirred evenly; at 85-95° C., a mixed solution of fluorinated epoxy resin and liquid fluorosilicone resin is added dropwise to the fluorinated low molecular weight polyamine at a ratio of 1:0.8-1.2 within 1-3 hours, and the mixture is kept warm for reaction at 90-95° C. for 2-4 hours; then, a silicon-containing glycidyl ether capping agent is added dropwise within 1-2 hours at a ratio of 1:0.8-1.2 of the amount of the silicon-containing glycidyl ether capping agent to the fluorinated low molecular weight polyamine; the mixture is kept warm for reaction for 3-5 hours; the mixture is cooled to room temperature; an acidic neutralizer is added at a ratio of 1:0.4-0.8 of the amount of the neutralizer to the fluorinated low molecular weight polyamine; and finally, 60-100 parts by weight of deionized water are added for dilution to obtain a water-based fluorinated silicon epoxy curing agent.

[0034] (3) Preparation of micro-nanoparticle modified slurry

[0035] Add 5 parts by mass of micro-nano particles, 50 parts by mass of deionized water and 0.5-1.5 parts by mass of a mixed solution of a fluorinated silane coupling agent to a four-necked flask equipped with a stirring device, a thermometer and a condenser, heat to 105°C, and reflux for 12-24 hours. After cooling to room temperature, the product is transferred to a rotary evaporator, and the deionized water is removed by heating and distillation. Add silicon-containing glycidyl ether, and ultrasonically disperse for 1-2 hours to obtain a micro-nano particle modified slurry with a solid content of 15-30%.

[0036] (4) Preparation of water-based super-hydrophobic binder for TIT embedding sealant

[0037] Add 100 parts by mass of the above-mentioned fluorine-containing silicon epoxy resin emulsion, 80-100 parts by mass of the above-mentioned water-based fluorine-containing silicon epoxy curing agent, 20-50 parts by mass of the above-mentioned micro-nano particle modified slurry, 0.2-0.5 parts by mass of leveling agent and 0.3-1.0 parts by mass of defoaming agent into a stirring kettle, stir evenly, and filter to obtain a water-based super-hydrophobic consolidating material for the TIT embedded sealing layer.

[0038] The fluorinated epoxy resin is one of diphenol hexafluoropropane diglycidyl ether, 1,4-bis(hydroxyhexafluoroisopropyl)benzene diglycidyl ether and 4,4'-dihydroxyoctafluorobiphenyl diglycidyl ether.

[0039] The liquid fluorosilicone resin is a liquid fluorosilicone resin with a viscosity of 50-200 mPa.s.

[0040] The carboxyl functional monomer is one of methacryloyloxyethyl maleic acid monoester, methacryloyloxyethyl phthalic acid monoester and methacryloyloxyethyl hexahydrophthalic acid monoester.

[0041] The antioxidant is one of pentaerythritol tetrakis[β-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate, n-octadecylβ-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate, 1,1,3-tris(2-methyl-4-hydroxy-5-tert-butylphenyl)butane, 2,6-di-tert-butyl-4-methylphenol, and dilauryl thiodipropionate.

[0042] The anti-ultraviolet agent is one of 2-hydroxy-4-methoxybenzophenone, 2,2'-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-n-octyloxybenzophenone, 2-hydroxybenzoic acid-4-(1,1-dimethylethyl)phenyl ester, salicylic acid n-octylphenyl ester, 2'-(2'-hydroxy-3'-tert-butyl-5'-methylphenyl)-5-chlorobenzotriazole, and 2-(2'-hydroxy-3',5'-di-tert-butylphenyl)-5-chlorobenzotriazole.

[0043] The initiator is one of azobisisobutyronitrile, azobisisoheptanenitrile, dimethyl azobisisobutyrate, dibenzoyl peroxide, and dilauroyl peroxide.

[0044] The alkaline neutralizing agent is one of triethylamine, triethanolamine, N-methyldiethanolamine and N-ethyldiethanolamine.

[0045] The fluorine-containing low molecular weight polyamine is a fluorine-containing diamine, preferably 2,2-bis[4-(4-aminophenoxy)phenyl]hexafluoropropane.

[0046] The silicon-containing glycidyl ether capping agent is a glycidyl ether containing silicon element, preferably tert-butyl dimethylsilyl glycidyl ether.

[0047] The acidic neutralizer is a low molecular weight organic acid, preferably glacial acetic acid.

[0048] The micro-nano particles are one of micro-nano titanium dioxide, micro-nano silicon dioxide and micro-nano kaolin.

[0049] The fluorine-containing silane coupling agent is one of heptadecafluorodecyltrimethoxysilane and tridecafluorooctyltriethoxysilane.

[0050] Example 1

[0051] (1) Preparation of fluorinated silicone epoxy resin emulsion

[0052] 70 parts by mass of diphenol hexafluoropropane diglycidyl ether and 30 parts by mass of liquid fluorosilicone resin with a viscosity of 50 mPa.s were put into a stirred reactor, the temperature was raised to 70°C, 10 parts by mass of methacryloyloxyethyl maleate, 1 part by mass of β-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate, 1 part by mass of octadecyl alcohol, 1 part by mass of 2-hydroxybenzoic acid-4-(1,1-dimethylethyl)phenyl ester and 1 part by mass of azobisisoheptonitrile were added, the reaction was carried out for 3 hours, the mixture was cooled to room temperature, 5.2 parts by mass of N-methyldiethanolamine was added, and then 80 parts by mass of deionized water were added under high-speed stirring, and the phase was inverted to obtain a uniform white liquid, thereby preparing a fluorine-containing silicone epoxy resin emulsion.

[0053] (2) Preparation of water-based fluorinated silicon epoxy curing agent

[0054] 50 parts by mass of diphenol hexafluoropropane diglycidyl ether and 50 parts by mass of liquid fluorosilicone resin with a viscosity of 50 mPa.s are put into a stirred reactor and stirred to obtain a mixture; the above mixture is added dropwise to 83 parts by mass of 2,2-bis[4-(4-aminophenoxy)phenyl]hexafluoropropane at 85° C. within 1 hour, and the mixture is kept warm at 90° C. for reaction for 4 hours, and then 80 parts by mass of tert-butyldimethylsilyl glycidyl ether is added dropwise within 1 hour, and the reaction is continued for 5 hours after the mixture is kept warm. The mixture is cooled to room temperature, 1 part by mass of glacial acetic acid is added, and finally 60 parts by mass of deionized water are added for dilution to obtain a water-based fluorine-containing silicon epoxy curing agent.

[0055] (3) Preparation of micro-nanoparticle modified slurry

[0056] In a four-necked flask equipped with a stirring device, a thermometer and a condenser, 5 parts by mass of silica micro-nano particles, 50 parts by mass of deionized water and 0.5 parts by mass of a mixed solution of tridecafluorooctyl triethoxysilane were added, heated to 105°C, and refluxed for 24 hours. After cooling to room temperature, the product was transferred to a rotary evaporator, and the deionized water was removed by heating and distillation. 28.5 parts by mass of tert-butyl dimethylsilyl glycidyl ether was added, and ultrasonic dispersion was performed for 1 hour to obtain a micro-nano particle modified slurry.

[0057] (4) Preparation of water-based super-hydrophobic binder for TIT embedding sealant

[0058] Add 100 parts by mass of the above-mentioned fluorine-containing silicon epoxy resin emulsion, 80 parts by mass of the above-mentioned water-based fluorine-containing silicon epoxy curing agent, 20 parts by mass of the above-mentioned micro-nanoparticle modified slurry, 0.2 parts by mass of polyorganosiloxane leveling agent and 0.3 parts by mass of water-based defoaming agent into a stirring kettle, stir evenly, and filter to obtain a water-based super-hydrophobic consolidating material for the TIT embedded sealing layer.

[0059] Example 2

[0060] (1) Preparation of fluorinated silicone epoxy resin emulsion

[0061] 80 parts by mass of 1,4-bis(hydroxyhexafluoroisopropyl)benzene diglycidyl ether and 20 parts by mass of liquid fluorosilicone resin with a viscosity of 150 mPa.s were put into a stirred reactor, the temperature was raised to 80°C, 15 parts by mass of methacryloyloxyethyl phthalate, 2 parts by mass of dilauryl thiodipropionate, 2 parts by mass of 2'-(2'-hydroxy-3'-tert-butyl-5'-methylphenyl)-5-chlorobenzotriazole and 3 parts by mass of dilauroyl peroxide were added, the reaction was carried out for 4 hours, the mixture was cooled to room temperature, 8 parts by mass of triethanolamine was added, and then 100 parts by mass of deionized water were added under high-speed stirring, and the phase was inverted to obtain a uniform white liquid, thereby preparing a fluorine-containing silicone epoxy resin emulsion.

[0062] (2) Preparation of water-based fluorinated silicon epoxy curing agent

[0063] 65 parts by mass of 1,4-bis(hydroxyhexafluoroisopropyl)benzene diglycidyl ether and 35 parts by mass of liquid fluorosilicone resin with a viscosity of 150 mPa.s were put into a stirred reactor and stirred evenly; the mixed solution was added dropwise to 85 parts by mass of 2,2-bis[4-(4-aminophenoxy)phenyl]hexafluoropropane at 90° C., and the mixture was kept warm for reaction at 92° C. for 3 hours, and then 80 parts by mass of tert-butyldimethylsilyl glycidyl ether was added dropwise within 1.5 hours, and the reaction was continued for 4 hours after keeping warm, and the mixture was cooled to room temperature, 2 parts by mass of glacial acetic acid was added, and finally 80 parts by mass of deionized water were added for dilution to obtain a water-based fluorine-containing silicon epoxy curing agent.

[0064] (3) Preparation of micro-nanoparticle modified slurry

[0065] In a four-necked flask equipped with a stirring device, a thermometer and a condenser, 5 parts by mass of micro-nano silica particles, 50 parts by mass of deionized water and 1 part by mass of a mixed solution of heptadecafluorodecyltrimethoxysilane were added, heated to 105°C, and refluxed for 18 hours. After cooling to room temperature, the product was transferred to a rotary evaporator, and the deionized water was removed by heating and distillation. 20 parts by mass of tert-butyl dimethylsilyl glycidyl ether was added, and ultrasonic dispersion was performed for 1.5 hours to obtain a micro-nano particle modified slurry.

[0066] (4) Preparation of water-based super-hydrophobic binder for TIT embedding sealant

[0067] Add 100 parts by mass of the above-mentioned fluorine-containing silicon epoxy resin emulsion, 90 parts by mass of the above-mentioned water-based fluorine-containing silicon epoxy curing agent, 35 parts by mass of the above-mentioned micro-nanoparticle modified slurry, 0.4 parts by mass of polyorganosiloxane leveling agent and 0.7 parts by mass of water-based defoaming agent into a stirring kettle, stir evenly, and filter to obtain a water-based super-hydrophobic consolidating material for the TIT embedded sealing layer.

[0068] Example 3

[0069] (1) Preparation of fluorinated silicone epoxy resin emulsion

[0070] 90 parts by mass of 4,4'-dihydroxyoctafluorobiphenyl diglycidyl ether and 10 parts by mass of liquid fluorosilicone resin with a viscosity of 200 mPa.s were put into a stirred reactor, the temperature was raised to 90°C, 20 parts by mass of methacryloyloxyethyl hexahydrophthalic acid monoester, 3 parts by mass of pentaerythritol tetrakis[β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate, 3 parts by mass of 2-(2'-hydroxy-3',5'-di-tert-butylphenyl)-5-chlorobenzotriazole, and 5 parts by mass of dimethyl azobisisobutyrate were added, the reaction was carried out for 5 hours, the reaction was cooled to room temperature, 9.6 parts by mass of N-ethyldiethanolamine was added, and then 120 parts by mass of deionized water were added under high-speed stirring, and the phase was inverted to obtain a uniform white liquid, thereby preparing a fluorine-containing silicone epoxy resin emulsion.

[0071] (2) Preparation of water-based fluorinated silicon epoxy curing agent

[0072] 80 parts by mass of 4,4'-dihydroxyoctafluorobiphenyl diglycidyl ether and 20 parts by mass of liquid fluorosilicone resin with a viscosity of 200 mPa.s are put into a stirred reactor and stirred evenly; 92 parts by mass of 2,2-bis[4-(4-aminophenoxy)phenyl]hexafluoropropane are added dropwise at 95°C within 1 hour, and the mixture is kept warm for reaction at 95°C for 2 hours, and then 88 parts by mass of tert-butyldimethylsilyl glycidyl ether are added dropwise within 2 hours, and the mixture is kept warm for reaction for 3 hours, cooled to room temperature, 3 parts by mass of glacial acetic acid are added, and finally 100 parts by mass of deionized water are added for dilution to obtain a water-based fluorine-containing silicon epoxy curing agent.

[0073] (3) Preparation of micro-nanoparticle modified slurry

[0074] In a four-necked flask equipped with a stirring device, a thermometer and a condenser, 5 parts by mass of micro-nano kaolin particles, 50 parts by mass of deionized water and 1.5 parts by mass of a mixed solution of heptadecafluorodecyltrimethoxysilane were added, heated to 105°C, and refluxed for 12 hours. After cooling to room temperature, the product was transferred to a rotary evaporator, and the deionized water was removed by heating and distillation. 12 parts by mass of tert-butyldimethylsilyl glycidyl ether was added, and ultrasonic dispersion was performed for 2 hours to obtain a micro-nano particle modified slurry.

[0075] (4) Preparation of water-based super-hydrophobic binder for TIT embedding sealant

[0076] Add 100 parts by mass of the above-mentioned fluorine-containing silicon epoxy resin emulsion, 100 parts by mass of the above-mentioned water-based fluorine-containing silicon epoxy curing agent, 50 parts by mass of the above-mentioned micro-nano particle modified slurry, 0.5 parts by mass of polyorganosiloxane leveling agent and 1.0 parts by mass of water-based defoaming agent into a stirring kettle, stir evenly, and filter to obtain a water-based super-hydrophobic consolidating material for the TIT embedded sealing layer.

[0077] Comparative Example 1

[0078] (1) Preparation of epoxy resin emulsion: 10 parts by weight of nonionic emulsifier and 100 parts by weight of epoxy resin E-51 were placed in a stirred reactor, the temperature was raised to 70° C., and 80 parts by weight of deionized water were slowly added under high-speed stirring until a uniform white liquid was formed, thereby obtaining the epoxy resin emulsion.

[0079] (2) Preparation of waterborne epoxy curing agent: 100 parts by weight of E-51 was added dropwise to 42 parts by weight of diethylenetriamine in a reaction kettle at 85° C. within 1 hour, and the mixture was kept warm at 90° C. for 4 hours. Then, 80 parts by weight of butyl glycidyl ether was added dropwise within 1 hour, and the mixture was kept warm for 5 hours. The mixture was cooled to room temperature, 5 parts by weight of glacial acetic acid was added, and finally, 60 parts by weight of deionized water was added for dilution to obtain a waterborne epoxy curing agent having a solid content of 50%;

[0080] (3) Preparation of aqueous solidifying material for TIT embedded sealing layer: 100 parts by weight of the above-mentioned epoxy resin emulsion, 80 parts by weight of the above-mentioned water-based epoxy curing agent, 0.2 parts by weight of polysiloxane leveling agent and 0.3 parts by weight of aqueous defoaming agent were added into a stirring kettle, stirred evenly, and filtered to obtain aqueous solidifying material for TIT embedded sealing layer.

[0081] After the water-based consolidating material is cured, the performance test results are shown in Table 1:

[0082] Table 1

[0083] Test items Hydrophobic angle / ° hardness Artificial aging / h Pull-out strength / MPa Pendulum friction value Example 1 157 3H 1600 2.9 84 Example 2 156 3H 1800 2.8 83 Example 3 158 4H 1900 2.8 85 Comparative Example 1 85 1H 800 0.7 45

[0084] As can be seen from Table 1: after the water-based super-hydrophobic consolidating material is cured, the hydrophobic angle, hardness, aging resistance, adhesion and abrasion resistance of Examples 1-3 are significantly improved compared with Comparative Example 1, because the introduction of fluorinated epoxy resin, liquid fluorosilicone resin, fluorine-containing low molecular weight polyamine, silicon-containing glycidyl ether, and micro-nano particles / fluorine-containing silane coupling agent modified slurry reduces the surface energy of the coating film after curing; under the action of the micro-nano particles modified by the fluorine-containing silane coupling agent, the coating presents a papillary structure similar to that of a lotus leaf, so that the coating achieves a super-hydrophobic effect; through the curing action of the water-based fluorine-containing silicon epoxy curing agent and the fluorine-containing silicon epoxy resin emulsion, the cross-linking degree of the coating is improved, and the adhesion, wear resistance and aging resistance of the cured film are further improved, so that the water-based super-hydrophobic consolidating material for the TIT embedded sealing layer can meet the use requirements under different conditions.

[0085] Example 1: The super-hydrophobic layer after the super-hydrophobic consolidating material is coated on the concrete pavement and cured is subjected to sandpaper friction under the weight of a 300g or 1000g weight. Figure 1 As shown, Figure 2The contact angle test results of the test sample after 0 to 100 cycles of friction under the action of 300g weight; Figure 3 The contact angle and deicing force after the sample is rubbed for 0 to 50 cycles under the action of a 1000g weight. Figure 2 It can be seen that the contact angle of the sample without friction is 157°, and after 100 cycles under the action of 300g weight, it is 152°, which is only 3% lower. Figure 3 It can be seen that the contact angle and deicing force of the unfriction sample surface are 157° and 25±1.4kPa respectively. However, the bonding strength between the hydrophilic concrete and the ice cubes is greater than 815±6.7kPa, which indicates that the superhydrophobic surface can effectively reduce the adhesion of ice cubes. After 10 cycles of friction under a pressure of 1000g, the surface contact angle is 151°, a decrease of 4%, and the deicing force increases to 85kPa. This shows that the superhydrophobic layer of the TIT embedded sealing layer of the present invention after being cured with a water-based superhydrophobic consolidating material has a sustained and stable anti-icing effect.

[0086] The water-based super-hydrophobic consolidating material for the TIT embedded sealing layer of the present invention has excellent performance, good system compatibility, high production efficiency, easy industrialization, and wide application. No toxic solvent is released during the entire process, and the invention is a non-toxic, pollution-free, and environmentally friendly consolidating material for the TIT embedded sealing layer.

[0087] The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention. For those skilled in the art, the present invention may have various modifications and variations. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention shall be included in the protection scope of the present invention.

Claims

1. A water-based super-hydrophobic consolidating material for TIT embedding sealing layer, characterized in that include: Water-based fluorinated silicon epoxy curing agent, fluorinated silicon epoxy resin emulsion, leveling agent, defoaming agent and micro-nano particle modified slurry. After the embedded seal layer is cured with water-based super-hydrophobic consolidating material, the contact angle is greater than 150°, the hardness is greater than 4H, the artificial aging time is greater than 1500h, the pull-out strength is greater than 2MPa, and the pendulum friction value is ≥70; The water-based fluorinated silicon epoxy curing agent is prepared by the following method: (1) Add 50 to 80 parts by weight of fluorinated epoxy resin and 20 to 50 parts by weight of liquid fluorosilicone resin into a stirred reactor and stir evenly; (2) adding a mixture of fluorinated epoxy resin and liquid fluorosilicone resin to a fluorinated low molecular weight polyamine at 85 to 95°C within 1 to 3 hours, and reacting at 90 to 95°C for 2 to 4 hours, wherein the molar ratio of epoxy groups of the fluorinated epoxy resin to the fluorinated low molecular weight polyamine is 1:0.8 to 1.2; (3) Add the silicon-containing glycidyl ether capping agent dropwise to the mixed solution of (2) within 1 to 2 hours, and continue to keep the temperature to react for 3 to 5 hours. The ratio of the silicon-containing glycidyl ether capping agent to the fluorine-containing low molecular weight polyamine substance is 1:0.8 to 1.2; (4) cooling the mixed solution of (3) to room temperature, adding an acidic neutralizer, wherein the ratio of the neutralizer to the fluorine-containing low molecular weight polyamine substance is 1:0.4-0.8, and finally diluting with 60-100 parts by weight of deionized water to prepare a water-based fluorine-containing silicon epoxy curing agent; The fluorine-containing silicon epoxy resin emulsion is prepared by the following method: 70 to 90 parts by weight of fluorinated epoxy resin and 10 to 30 parts by weight of liquid fluorine silicon resin are put into a stirred reaction kettle, the temperature is raised to 70 to 90° C., 10 to 20 parts by weight of carboxyl functional monomers, 1 to 3 parts by weight of antioxidants, 1 to 3 parts by weight of anti-ultraviolet agents, and 1 to 5 parts by weight of initiators are added, the reaction is carried out for 3 to 5 hours, the mixture is cooled to room temperature, an alkaline neutralizer in an amount equal to that of the carboxyl functional monomers and other substances is added, and then 80 to 120 parts by weight of deionized water are added under high-speed stirring, and the phases are inverted to obtain a uniform white liquid, thereby obtaining the fluorine-containing silicon epoxy resin emulsion.

2. The aqueous super-hydrophobic consolidating material for the TIT embedding sealing layer according to claim 1, characterized in that: The mass ratio of the water-based fluorine-containing silicon epoxy curing agent, the fluorine-containing silicon epoxy resin emulsion, the leveling agent, the defoaming agent and the micro-nano particle modified slurry is (80-100):100:(0.2-0.5):(0.3-1.0):(20-50).

3. The aqueous super-hydrophobic consolidating material for TIT embedding sealing layer according to claim 1, characterized in that: The fluorinated epoxy resin is diphenol hexafluoropropane diglycidyl ether, 1,4-bis(hydroxyhexafluoroisopropyl)benzene diglycidyl ether or 4,4'-dihydroxyoctafluorobiphenyl diglycidyl ether; the liquid fluorosilicone resin has a viscosity of 50 to 200 mPa·s; the silicon-containing glycidyl ether capping agent is tert-butyl dimethylsilyl glycidyl ether; and the acidic neutralizing agent is glacial acetic acid.

4. The aqueous super-hydrophobic consolidating material for TIT embedding sealing layer according to claim 1, characterized in that: The fluorine-containing low-molecular polyamine is 2,2-bis[4-(4-aminophenoxy)phenyl]hexafluoropropane.

5. The aqueous super-hydrophobic consolidating material for TIT embedding sealing layer according to claim 1, characterized in that: The fluorinated epoxy resin is diphenol hexafluoropropane diglycidyl ether, 1,4-bis(hydroxyhexafluoroisopropyl)benzene diglycidyl ether or 4,4'-dihydroxyoctafluorobiphenyl diglycidyl ether; the liquid fluorosilicone resin has a viscosity of 50 to 200 mPa·s; the carboxyl functional monomer is methacryloyloxyethyl maleic acid monoester, methacryloyloxyethyl phthalic acid monoester or methacryloyloxyethyl hexahydrophthalic acid monoester; the antioxidant is tetrakis[β-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate] pentaerythritol ester, β-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate n-octadecyl alcohol ester, 1,1,3-tris(2-methyl-4-hydroxy-5-tert-butylphenyl)butane, 2,6-di-tert-butyl-4-methyl Phenol or dilauryl thiodipropionate; the anti-ultraviolet agent is 2-hydroxy-4-methoxybenzophenone, 2,2'-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-n-octyloxybenzophenone, 2-hydroxybenzoic acid-4-(1,1-dimethylethyl)phenyl ester, n-octylphenyl salicylate, 2'-(2'-hydroxy-3'-tert-butyl-5'-methylphenyl)-5-chlorobenzotriazole or 2-(2'-hydroxy-3',5'-di-tert-butylphenyl)-5-chlorobenzotriazole; the initiator is azobisisobutyronitrile, azobisisoheptylnitrile, dimethyl azobisisobutyrate, dibenzoyl peroxide or dilauroyl peroxide; the alkaline neutralizer is triethylamine, triethanolamine, N-methyldiethanolamine or N-ethyldiethanolamine.

6. The aqueous super-hydrophobic consolidating material for TIT embedding sealing layer according to claim 1, characterized in that: The leveling agent is one of polyorganosiloxane, polyether-modified polyorganosiloxane or fluorine-containing surfactant, and the defoamer is an aqueous defoamer.

7. The aqueous super-hydrophobic consolidating material for TIT embedding sealing layer according to claim 1, characterized in that: The micro-nano particle modified slurry is prepared by the following method: 5 parts by mass of micro-nano particles, 50 parts by mass of deionized water and a mixed solution of 0.5-1.5 parts by mass of a fluorine-containing silane coupling agent are added to a four-necked flask equipped with a stirring device, a thermometer and a condenser, heated to 105° C., and refluxed for 12-24 hours; after cooling to room temperature, the product is transferred to a rotary evaporator, and the deionized water is removed by heating and distillation; silicon-containing glycidyl ether is added, and ultrasonic dispersion is performed for 1-2 hours to obtain a micro-nano particle modified slurry with a solid content of 15%-30%.

8. The aqueous super-hydrophobic consolidating material for TIT embedding sealing layer according to claim 7, characterized in that: The micro-nano particles are micro-nano titanium dioxide, micro-nano silicon dioxide or micro-nano kaolin; the fluorine-containing silane coupling agent is heptadecafluorodecyltrimethoxysilane or tridecafluorooctyltriethoxysilane; and the silicon-containing glycidyl ether is tert-butyl dimethylsilyl glycidyl ether.

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