KR20230019494A - Deterioration immune bionic protective coating layer used in repair process and manufacturing method thereof - Google Patents

Abstract

The present invention discloses a deterioration immune bionic protective coating layer and manufacturing method used in a repair process. The degradation immune bionic protective coating layer is a protective coating layer of a concrete matrix, and the degradation immune bionic protective coating layer is composed of two layers, that is, a primer and a top coat; Interdiffusion between the two layers occurs and chemical crosslinking occurs, and molecules are crosslinked to form an interpenetrating network. The primer is a self-healing epoxy powder or a self-healing epoxy solution obtained by uniformly dispersing GO-modified polyurea-based double-walled microcapsules and polydopamine in an epoxy resin, and the primer is a coating film. The thickness to form is 250 to 1000 μm; The top coat is a polyurethane/polyurea solution in which a two-dimensional material is combined, and the thickness at which the top coat forms a film is 100 to 2000 μm. The deterioration immune bionic protective coating layer used in the repair process restores physical cracks and protects concrete from two aspects of resisting chemical erosion to realize immunity to deterioration of the concrete structure, and the protective coating layer according to the prior art is easily damaged and It achieves important economic values and social effects by resolving irreparable defects.

Description

Deterioration immune bionic protective coating layer used in repair process and manufacturing method thereof

The present invention belongs to the field of materials and relates to a protective coating layer and a manufacturing method thereof, and in detail, to a deterioration immune bionic protective coating layer of a repair process structure and a manufacturing method thereof.

As the size of the city expands and the industry develops, the discharge of domestic sewage and industrial wastewater has increased markedly, and surface water has been polluted on a different level, and the content of highly corrosive substances such as acids, alkalis, salts, and organic matter in sewage has increased significantly. there is. In the repair process, structural members are immersed in water for a long time, especially in bad conditions such as always dark, wet, dry and wet, and eroded by water current, so the level of destruction of reinforced concrete members in the repair process Each is different, and corrosive media such as sulfate, carbonate, magnesium salt and chloride in sewage not only affect the durability of the concrete itself, but also destroy the stabilized film on the surface of the reinforcing bar, corroding and destroying the reinforcing bar. According to the statistical results of the United States (FHWA), more than 50% of nearly 600,000 bridges in the United States have been found to have pests that cause corrosion of reinforcing bars, and maintenance costs of 75 billion dollars are required every year. In Japan, restoration costs currently used for reinforced concrete facilities far exceed their construction costs. Therefore, the multi-corrosion prevention technology of reinforced concrete placed in the sewage environment has a very important significance in enhancing the durability of buildings and maintaining safe operation of the process.

In the repair process structure, simultaneously protecting the concrete and the reinforcing bars so as to increase the service life of the reinforced concrete material is a key point to protect the entire life of the repair process concrete structure. As the corrosion mechanism and protection technology of reinforced concrete develop rapidly, the protection technology of reinforced concrete already has various protection technologies such as concrete outer protective coating layer, steel rust prevention/corrosive agent addition, cathodic protection and reinforcement coating layer protection. was formed Compared with other protective technologies, the protective technology of the concrete surface coating layer can very well inhibit the penetration of corrosive ions in the external environment, completely isolate the reinforced concrete matrix from the external environment, and provide excellent anti-corrosion protection. If the coating layer adheres to the concrete matrix and does not lose its effectiveness and is not destroyed, it can continue to provide excellent protection for concrete and reinforcing bars. However, in the actual application process, it is difficult to protect the concrete surface coating layer protection technology during the entire life cycle, for the following reasons. (1) Since the adhesive force between the coating layer and the concrete interface is relatively weak, adhesive detachment easily occurs when an external load acts; (2) Most of the conventional reinforced concrete coating layer protection is an epoxy coating layer, which has high hardness and strong brittleness; When processing at the construction site, the coating layer is easily destroyed; In other words, the conventional coating layer protection technology cannot consider mechanical performance and processability together. In the coating layer protection technology, as long as the coating layer is locally damaged, the corrosive medium will invade from the broken point, and the entire coating layer protection system will lose its effectiveness; (3) The conventional coating layer protection technology can only provide anti-corrosion protection by isolating the reinforced concrete matrix, and repair and immunity to cracks and erosion factors cannot be considered together.

In order to solve the problem existing in the conventional concrete coating layer protection technology, the present invention discloses a deterioration immune bionic protective coating layer used in a repair process. The degradation immune bionic protective coating layer imitates the human immune system and realizes bionic immune anti-corrosion treatment for concrete through the optimization design of the concrete coating layer structure.

In the technical solution of the present invention, a method for manufacturing a degradation immune bionic protective coating layer used in a water repair process includes the following steps.

(1) pre-treating the concrete surface:

(1a) The concrete surface is treated to make the concrete surface clean and flat to reach a certain surface roughness. The specific method is as follows, removing dust, debris and surface grime from the surface; Remove the damaged and vulnerable concrete surface layer, and restore uneven points on the concrete surface using a restoration agent or mortar; By treating the concrete surface, the surface roughness of the concrete is increased to secure the adhesion between the coating layer and the concrete.

(1b) The concrete surface is immersed with a silane emulsion, the temperature of the concrete surface during the immersion period is 5 to 40 ° C, and the depth of concrete immersion is 1 to 4 mm. The silane emulsion is obtained by hydrolyzing silane monomers; The silane monomer is among triethoxyvinylsilane, trimethoxyvinylsilane, triethoxymethylsilane, triethoxyoctylsilane, and triethoxyisobutylsilane. one or several By immersing and treating the surface of concrete with silane, the amino group, epoxy group or unsaturated double bond of one end of the silane coupling agent can participate in the curing reaction of the primer; At the same time, a dehydration reaction occurs on the concrete surface with a silanol group, which is another hydrolysis product of the coupling agent, to form a chemical bond so that the concrete and the primer are chemically interconnected through the coupling agent, Furthermore, the cohesive force of the interface is improved.

(2) preparing a non-specific stress self-healing immune layer:

After completing the pre-treatment of the concrete in step (1), heating to 25 to 60 ° C., and then spray-coating the primer to obtain a non-specific stress self-healing immune layer; The thickness at which the primer forms a film is 250 to 1000 μm; The primer is an epoxy resin, and the manufacturing method is as follows.

(2a) preparing GO-modified polyurea-based double-walled microcapsules; GO-modified double-walled polyurea microcapsules/epoxy composites for marine anticorrosive self-healing coating.( Materials & Design , Ma Y, Zhang Y, Liu J, et al. 2020, 189: 108547). Polyurea-based double-walled microcapsules modified with graphene are prepared.

(2b) preparing polydopamine microspheres; Polydopamine is prepared using a water-phase oxidation method, an ethanol solution and ammonia solution of a certain concentration are stirred at 40 to 50 ° C, a certain amount of dopamine hydrochloride solution is added, stirred, and react for 10 h; After the reaction is complete, centrifugal washing is performed to obtain polydopamine microspheres.

(2c) preparing a self-healing epoxy powder or epoxy solution; GO-modified polyurea-based double-walled microcapsules obtained in step (2a), polydopamine microspheres obtained in step (2b), and epoxy resin curing agent I were added to the powdery epoxy resin and uniformly dispersing to obtain a self-healing epoxy powder; Alternatively, the GO-modified polyurea-based double-walled microcapsules obtained in step (2a) and the polydopamine microspares obtained in step (2b) are added to an epoxy resin solution and dispersed at high speed to ensure uniform mixing of the system, ; After the dispersion is completed, the epoxy resin curing agent II is added and stirred uniformly to obtain a self-healing epoxy solution. In the prepared self-healing epoxy powder or self-restoring epoxy solution, the polydopamine microspheres and GO-modified polyurea-based double-walled microcapsules are added in an amount of 0.5 to 10 wt% of the epoxy resin. The self-healing epoxy powder or epoxy solution binds the extrinsic self-healing double-walled microcapsule and the intrinsic self-healing means, but the damaged microcapsule releases the restoring agent to restore the damage. In addition, by forming a hydrogen bond between polydopamine molecules, the cavity left after the microcapsule is released and the damaged area of the microcapsule that is not triggered are restored, and furthermore, the self-restoration of the primer efficiency can be improved.

Here, the model of the epoxy resin is E-44, E51 or E-54. The epoxy resin curing agent I is one of dicyandiamide, dicyandiamide derivative, acid anhydride, imidazole, cyclic ether and phenolic resin, or It is several. The epoxy resin curing agent II is a polyamide resin, ethylene diamine, diethylenetriamine, tetraethylenepentamine, maleic anhydride and phthalic anhydride one or several

A specific method of spray coating the primer,

(1) Using the hot melt spray coating method, in detail, adding self-healing epoxy powder to the hot melt spray coating machine, heating it to 140 to 200 ° C, and using a spray gun to coat the concrete. Spray coating uniformly on the surface;

or (2) use the method of spray coating or brush coating of the solution, specifically, add a certain amount of solvent to the self-healing epoxy solution to make the primer reach the spray coating standard; Then, it is spray-coated or brush-coated uniformly on the concrete surface; The solvent is xylene, 1-butanol, or a mixed solution of both.

(3) Preparing a non-specific damaged self-differentiation immune layer:

After completing the spray coating of the undercoat, the surface temperature is maintained at not lower than 30 ° C, and immediately proceeds with the spray coating of the topcoat to obtain a non-specific damage self-differentiation immune layer, thereby reducing the deterioration immune bionic protective coating layer. complete the manufacturing The thickness at which the top coat forms a film is 100 to 2000 μm; The top coat is a polyurethane/polyurea solution in which a two-dimensional material is combined, and the manufacturing method is as follows, uniformly mixing polyether, solvent I and emulsifier, and vacuuming at 100 to 120 ° C. for 1 to 3 h. Dehydrated, then cooled to 20 to 65° C., slowly added an Isocyanate monomer, and prepolymerized for 5 to 60 min to obtain a prepolymer. Two-dimensional material, ultraviolet light stabilizer, heat stabilizer, polyester polyol and amino group chain extender are added to solvent II, mixed uniformly, and then added to the pre-polymer again, and warmed to 0.5 to 3 h to obtain a polyurethane/polyurea solution in which two-dimensional materials are combined. The coating layer matrix of the top coat is pure polyurethane, hybrid polyurethane-hybrid polyurea, or pure polyurea solution. When the coating layer matrix uses polyurethane as a main material, the polyether used is polyether polyalcohol; When polyurea is used as a main material, the polyether used is polyether amine. The two-dimensional material of the top coat is distributed in a layer form to block or extend the penetration path of the corrosive medium and improve the durability of the concrete material to be protected; The light stabilizer and heat stabilizer of the top coat can improve the aging resistance of the coating layer.

Here, the equivalence ratio of the hydroxyl group of the polyester polyol-amino group chain extender and the functional group of “hydroxyl group + amino group” is (0-0.37): 1 and (0.48-1): 1, and the functional group equivalent ratio of -NCO and “hydroxyl group + amino group” in the reaction system is (1.05-1.2): 1, and the amount of the two-dimensional material is 0.5 to 15 wt% of the isocyanate monomer, and the The amount of the ultraviolet light stabilizer is 0.01 to 1 wt% of the isocyanate monomer, and the amount of the heat stabilizer is 0.05 to 5 wt% of the isocyanate monomer.

Here, the polyether polyalcohol is polyoxy propylene glycol, trihydroxymethylpropane polyether, polytetrahydrofuran glycol, tetrahydrofuran oxide-propylene copolymer one or more of glycol (tetrahydrofuranoxide propylene copolymer glycol) and polyoxyethylene glycol; the polyether amine is one or more of D230, D400, D2000, T403, and T5000; The two-dimensional material is one or more of graphene, mica, montmorillonite, graphite, and boron nitride; The isocyanate monomer is hexamethylene diisocyanate (HDI), dicyclohexylmethane diisocyanate (HMDI), methylene diphenyl diisocyanate (MDI), toluene diisocyanate (toluene one or more of diisocyanate (TDI) and isophorone diisocyanate (IPDI); The polyester polyol is ethylene glycol, diethylene glycol, 1,2-propanediol, dipropylene glycol, 1,4- Butanediol, neopentyl glycol, 1,6-hexanediol, adipic acid, trihydroxymethylpropane and isophthalic acid (iso phthalic acid); The amino group chain extender is diethyl toluene diamine, dimethyl thio toluene diamine, N, N'-dialkyl methyl diphenylamine (N, N'-dialkyl methyl diphenylamine), cyclohexanediamine, MDH chloride, ethylene diamine, 1,3-diaminopropane, 1,4-diaminobutane, Diethylenetriamine, pentaethylene hexamine, hexaethylene diamine, tetraethylenepentamine, 1,6-diaminohexane and 3, one or more of 3'-4,4'-diamino-diphenyl methane; The UV light stabilizer includes phenyl salicylate, salicylic acid-4-octylphenyl ester, resorcinol monobenzoate, 2-hydroxy-4- 2-hydroxy-4-methoxybenzophenone, 2,4-dihydroxybenzophenone and 2-hydroxy-4-octyloxy benzophenone benzophenone), one or more; The heat stabilizer is tribasic lead sulfate, dibasic lead phosphite, dibasic lead stearate, cadmium stearate, barium stearate, calcium stearate, stearic acid One or more of lead stearate, zinc stearate, fatty acid salt and maleate.

In the specific method of spray coating the top coat, a certain amount of solvent, that is, N-N-Dimethylacetamide, is added to the polyurethane/polyurea solution in which the two-dimensional material is combined to reach the spray coating standard. let it do; Then spray coat it evenly over the primer using a spray gun.

In the degradation immune bionic protective coating layer used in the repair process manufactured by the above method, the degradation immune bionic protective coating layer is a protective coating layer of a concrete matrix, and the degradation immune bionic protective coating layer has two layers, that is, a primer It consists of a top coat; interdiffusion between the two layers and chemical crosslinking occurs, molecules are crosslinked to form an interpenetrating network; The primer is a self-healing epoxy powder or a self-restoring epoxy solution obtained by uniformly dispersing GO-modified polyurea-based double-walled microcapsules and polydopamine in an epoxy resin, and the thickness of the primer to form a film is 250 to 1000 μm; The top coat is a polyurethane/polyurea solution in which a two-dimensional material is combined, and the thickness at which the top coat forms a film is 100 to 2000 μm.

Manufacturing principle: When the undercoat and topcoat are not completely cured, they are painted in sequence, so that the two layers of paint at the interface point inter-diffusion along the solvent, and the long chains of polymer molecules are short to interpenetrate, diffuse, and wind to interpenetrate. form a network Here, the epoxy group and the curing agent that have not completely reacted in the segment in which the undercoating agent is inter-diffused continue to react continuously with the amino group and -NCO of the opposite chain extender, so that chemical crosslinking occurs on the paint surface of the two layers, and finally On, it hardens and the molecules crosslink to obtain an interpenetrating network. Therefore, from an essential point of view, the two-layer structure of the degradation immune bionic protective coating layer is substantially very close and forms an inseparable layer. In addition, the surface of the concrete is treated by immersing in silane, and a dehydration reaction occurs on the surface of the concrete with a silanol group, which is a hydrolysis product of a coupling agent, to form a chemical bond; At the same time, the amino group, epoxy group or unsaturated double bond of the other end of the coupling agent can participate in the curing reaction of the primer, allowing the concrete and the primer to be chemically interconnected through the coupling agent, and furthermore, the cohesiveness of the interface improve

The present invention achieves the following advantageous effects.

(1) The deterioration immune bionic protective coating layer used in the repair process described in the present invention realizes immunity against deterioration of the concrete structure by restoring physical cracks and protecting concrete from two aspects of resisting chemical erosion. And, the protective coating layer according to the prior art is easily damaged and eliminates defects that cannot be restored, thereby achieving important economic values and social effects.

(2) The deterioration immune bionic protective coating layer used in the repair process described in the present invention is composed of two layers, that is, a primer and a top coat, and the two layers interpenetrate at the interface point to form a network interface in which molecules crosslink and interpenetrate. It solves the technical problem of weak interface by forming and integrating into a single unit .

(3) In the deterioration immune bionic protective coating layer used in the repair process described in the present invention, the surface of the concrete is immersed and treated with silane so that the concrete and the primer are chemically interconnected through a coupling agent, furthermore, the interface improve the cohesion of

1 is one of structural diagrams of a deterioration immune bionic protective coating layer according to the present invention;
Figure 2 is a structural explanatory diagram of a primer for a degradation immune bionic protective coating layer according to the present invention;
Figure 3 is a structural explanatory diagram of the top coat of the degradation immune bionic protective coating layer according to the present invention.

Hereinafter, the present invention will be further described by combining examples.

Example 1:

In the deterioration immune bionic protective coating layer used in the water repair process, the degradation immune bionic protective coating layer is a protective coating layer of a concrete matrix. The degradation immune bionic protective coating layer is composed of two layers, that is, a primer and a top coat; Interdiffusion between the two layers occurs and chemical crosslinking occurs, and molecules are crosslinked to form an interpenetrating network. The primer is a self-healing epoxy powder obtained by uniformly dispersing GO-modified polyurea-based double-walled microcapsules and polydopamine in an epoxy resin, and the thickness of the primer to form a film is 500 μm. is; The top coat is a polyurethane/polyurea solution in which a two-dimensional material is combined, and the thickness at which the top coat forms a film is 1000 μm. The manufacturing method is as follows.

(1) pre-treating the concrete surface:

(1a) The concrete surface is treated to make the concrete surface clean and flat to reach a certain surface roughness. The specific method is as follows, removing dust, debris and surface grime from the surface; Remove the damaged and vulnerable concrete surface layer, and restore uneven points on the concrete surface using a restoration agent or mortar; By treating the concrete surface, the surface roughness of the concrete is increased to secure the adhesion between the coating layer and the concrete.

(1b) The concrete surface is immersed using a silane emulsion, the temperature of the concrete surface during the immersion period is 25 ° C, and the depth of immersion in the concrete is 2 mm. The silane emulsion is obtained by hydrolyzing silane monomers; The silane monomer is triethoxyisobutylsilane.

(2) preparing a non-specific stress self-healing immune layer:

After completing the preliminary treatment of the concrete in step (1), heating to 55 ° C., and then spray-coating the primer to obtain a non-specific stress self-restoring immune layer; The primer is an epoxy resin, and the manufacturing method is as follows,

(2a) preparing GO-modified polyurea-based double-walled microcapsules; GO-modified double-walled polyurea microcapsules/epoxy composites for marine anticorrosive self-healing coating.( Materials & Design , Ma Y, Zhang Y, Liu J, et al. 2020, 189: 108547). Polyurea-based double-walled microcapsules modified with graphene are prepared.

(2b) preparing polydopamine microspheres; Polydopamine was prepared using a water-phase oxidation method, an ethanol solution and ammonia solution of a certain concentration were stirred at 45 ° C, a certain amount of dopamine hydrochloride solution was added, stirred and reacted for 10 h ; After the reaction is complete, centrifugal washing is performed to obtain polydopamine microspheres.

(2c) preparing a self-healing epoxy powder; GO-modified polyurea-based double-walled microcapsules obtained in step (2a), polydopamine microspheres obtained in step (2b) and epoxy resin curing agent I were added to the powdery epoxy resin and uniformly dispersed. obtain an epoxy powder of restoration; The amount of the polydopamine microspheres added was 2 wt% of the epoxy resin, and the amount of the GO-modified polyurea-based double-walled microcapsules was 3 wt% of the epoxy resin. Here, the model of the epoxy resin is E-44. The epoxy resin curing agent I is dicyandiamide.

The specific method of spray coating the primer is to use a hot melt spray coating method, in detail, add self-healing epoxy powder to a hot melt spray coater, heat it up to 140 ° C, and use a spray gun to concrete spray coat evenly on the surface of

(3) Preparing a non-specific damaged self-differentiation immune layer:

After completing the spray coating of the undercoat, the surface temperature is maintained at not lower than 30 ° C, and immediately proceeds with the spray coating of the topcoat to obtain a non-specific damage self-differentiation immune layer, thereby reducing the deterioration immune bionic protective coating layer. complete the manufacturing The top coat is polyurethane in which two-dimensional materials are combined, and the manufacturing method is as follows: polyether, solvent I and emulsifier are uniformly mixed, vacuum dehydrated at 105 ° C for 2 h, and then 55 ° C After cooling to , isocyanate monomer is slowly added, and pre-polymerization is performed for 5 min to obtain a pre-polymer. Two-dimensional material, ultraviolet light stabilizer, heat stabilizer, polyester polyol and amino group chain extender are added to solvent II, mixed uniformly, and then added to the pre-polymer again and kept warm for 2 h while reacting to obtain a polyurethane/polyurea solution in which two-dimensional materials are composited. The coating layer matrix of the top coat is pure polyurethane.

Here, the functional group equivalence ratio of the hydroxyl group of the polyester polyol-amino group chain extender and “hydroxyl group + amino group” is 1:1, and in the reaction system, -NCO and “hydrogen The functional group equivalent ratio of “oxyl group + amino group” is 1.05:1, the amount of the two-dimensional material is 1 wt% of the isocyanate monomer, the amount of the ultraviolet light stabilizer is 0.1 wt% of the isocyanate monomer, and the amount of the heat stabilizer is isocyanate It is 0.5wt% of the monomer.

Here, the polyether polyalcohol is polyoxy propylene glycol; The two-dimensional material is graphene; The isocyanate monomer is hexamethylene diisocyanate (HDI); the polyester polyol is ethylene glycol; The ultraviolet light stabilizer is phenyl salicylate; The amino group chain extender is 1,6-diaminohexane; The heat stabilizer is tribasic lead sulfate. The solvent I is N,N-dimethylacetamide, and the solvent II is N,N-dimethylacetamide.

The specific method of spray coating the top coat is to add a certain amount of solvent, that is, N-N-dimethylacetamide to the polyurethane solution in which the two-dimensional material is composited, so that the bottom coat reaches the spray coating standard; Then, spray coat it evenly with the primer using a spray gun.

Example 2:

The difference from Example 1 is that

In the degradation immune bionic protective coating layer, the primer is a self-healing epoxy solution obtained by uniformly dispersing GO-modified polyurea-based double-walled microcapsules and polydopamine in an epoxy resin, and the thickness at which the primer forms a film is 250 μm; The thickness at which the top coat forms a film is 1200 μm.

The manufacturing method is as follows.

(1) pre-treating the concrete surface:

(1a) Same as Example 1.

(1b) The concrete surface is immersed using a silane emulsion, the temperature of the concrete surface during the immersion period is 40 ° C, and the depth of concrete immersion is 1 mm.

(2) preparing a non-specific stress self-healing immune layer:

After completing the pre-treatment of the concrete in step (1), heating to 60 ° C., and then spray-coating the primer to obtain a non-specific stress self-restoring immune layer; The primer is an epoxy resin, and the manufacturing method is as follows,

(2a) Same as Example 1.

(2b) Same as Example 1.

(2c) preparing a self-healing epoxy solution; The GO-modified polyurea-based double-walled microcapsules obtained in step (2a) and the polydopamine microspheres obtained in step (2b) were added to an epoxy resin solution and dispersed at high speed to ensure uniform mixing of the system; After the dispersion is completed, the epoxy resin curing agent II is added and stirred uniformly to obtain a self-healing epoxy solution. The addition amount of the polydopamine microspheres was 10 wt% of the epoxy resin, and the addition amount of the GO-modified polyurea-based double-walled microcapsule was 6 wt% of the epoxy resin. Here, the model of the epoxy resin is E-44. The epoxy resin curing agent II is a polyamide resin.

The specific method of spray coating the primer is to use the spray coating method of the solution, in detail, add a certain amount of solvent to the self-healing epoxy solution to make the primer reach the spray coating standard; Then, it is spray-coated uniformly on the concrete surface; The solvent is xylene.

(3) Preparing a non-specific damaged self-differentiation immune layer:

The top coat is polyurethane/polyurea in which two-dimensional materials are combined, and the manufacturing method is as follows, uniformly mixing polyether, solvent I and emulsifier, vacuum dehydration at 120 ° C. for 1 h, and then, 65 ° C. cooled to , slowly added isocyanate monomer, and pre-polymerized for 30 min to obtain a free polymer. The two-dimensional material, ultraviolet light stabilizer, heat stabilizer, polyester polyol and amino group chain extender are added to solvent II, mixed uniformly, and then added to the pre-polymer, kept warm, and reacted for 0.5 h to obtain a two-dimensional material. A composite polyurethane/polyurea solution is obtained. The coating layer matrix of the top coat is a hybrid polyurethane-hybrid polyurea.

Here, the functional group equivalent ratio of the hydroxyl group of the polyester polyol-amino group chain extender and “hydroxyl group + amino group” is 0.48: 1, and the functional group equivalent ratio of -NCO and “hydroxyl group + amino group” in the reaction system is 1.1: 1, the amount of the two-dimensional material is 10wt% of the isocyanate monomer, the amount of the ultraviolet light stabilizer is 1wt% of the isocyanate monomer, and the amount of the heat stabilizer is 5wt% of the isocyanate monomer.

Here, the polyether is polyoxy propylene glycol; The two-dimensional material is graphene; the isocyanate monomer is hexamethylene diisocyanate (HDI); the polyester polyol is ethylene glycol; The ultraviolet light stabilizer is phenyl salicylate; The amino group chain extender is pentaethylene hexamine; The heat stabilizer is tribasic lead sulfate. The solvent I is N,N-dimethylacetamide, and the solvent II is N,N-dimethylacetamide. The solvent I is N,N-dimethylacetamide, and the solvent II is N,N-dimethylacetamide.

The specific method of spray coating the top coat is to add a certain amount of solvent, that is, N-N-dimethylacetamide to the polyurethane solution in which the two-dimensional material is composited, so that the bottom coat reaches the spray coating standard; Then spray coat it evenly over the primer using a spray gun.

Example 3:

The difference from Example 1 is that

In the degradation immune bionic protective coating layer, the primer is a self-healing epoxy solution obtained by uniformly dispersing GO-modified polyurea-based double-walled microcapsules and polydopamine in an epoxy resin, and the thickness at which the primer forms a film is 1000 μm; The thickness at which the top coat forms a film is 2000 μm.

The manufacturing method is as follows.

(1) pre-treating the concrete surface:

(1a) Same as Example 1.

(1b) The concrete surface is immersed using a silane emulsion, the temperature of the concrete surface during the immersion period is 5 ° C, and the depth of concrete immersion is 4 mm. The silane emulsion is obtained by hydrolyzing silane monomers; The silane monomer is trimethoxyvinylsilane.

(2) preparing a non-specific stress self-healing immune layer:

After completing the pre-treatment of the concrete in step (1), heating to 35 ° C., and then spray-coating the primer to obtain a non-specific stress self-restoring immune layer; The primer is an epoxy resin, and the manufacturing method is as follows,

(2a) Same as Example 1.

(2b) preparing polydopamine microspheres; polydopamine was prepared by water oxidation method, stirring an ethanol solution and aqueous ammonia at a constant concentration at 50 ° C, adding a certain amount of dopamine hydrochloride solution, stirring and reacting for 9 h; After the reaction is complete, centrifugal washing is performed to obtain polydopamine microspheres.

(2c) preparing a self-healing epoxy solution; The GO-modified polyurea-based double-walled microcapsules obtained in step (2a) and the polydopamine microspheres obtained in step (2b) were added to an epoxy resin solution and dispersed at high speed to ensure uniform mixing of the system; After the dispersion is completed, the epoxy resin curing agent II is added and stirred uniformly to obtain a self-healing epoxy solution. The addition amount of the polydopamine microspheres was 5 wt % of the epoxy resin, and the addition amount of the GO-modified polyurea-based double-walled microcapsule was 10 wt % of the epoxy resin. Here, the model of the epoxy resin is E51. The epoxy resin curing agent II is tetraethylenepentamine.

The specific method of spray coating the primer is to use the brush coating method of the solution. Specifically, a certain amount of solvent is added to the self-healing epoxy solution to make the primer reach the spray coating standard; Then, it was brush coated uniformly on the concrete surface; The solvent is 1-butanol.

(3) Preparing a non-specific damage self-differentiation immune layer:

After completing the spray coating of the undercoat, the surface temperature is maintained at not lower than 30 ° C, and immediately proceeds with the spray coating of the topcoat to obtain a non-specific damage self-differentiation immune layer, thereby reducing the deterioration immune bionic protective coating layer. complete the manufacturing The top coat is a polyurethane / polyurea solution in which a two-dimensional material is combined, and the manufacturing method is as follows, uniformly mixing polyether, solvent I and emulsifier, vacuum dehydration at 110 ° C. for 1 h, and then, 20 Cool to °C, add isocyanate monomer slowly, and polymerize in advance for 60 min to obtain a free polymer. The two-dimensional material, ultraviolet light stabilizer, heat stabilizer, polyester polyol and amino group chain extender are added to solvent II, mixed uniformly, and then added to the free polymer, kept warm, and reacted for 3 h to make the two-dimensional material composite. A polyurethane/polyurea solution was obtained. The coating layer matrix of the top coat is a hybrid polyurethane-hybrid polyurea.

Here, the functional group equivalent ratio of the hydroxyl group of the polyester polyol-amino group chain extender and “hydroxyl group + amino group” is 0.37: 1, and the functional group equivalent ratio of -NCO and “hydroxyl group + amino group” in the reaction system is 1.2: 1, the amount of the two-dimensional material is 5wt% of the isocyanate monomer, the amount of the ultraviolet light stabilizer is 0.01wt% of the isocyanate monomer, and the amount of the heat stabilizer is 1wt% of the isocyanate monomer.

wherein the polyether is D2000; The two-dimensional material is mica; The isocyanate monomer is toluene diisocyanate (TDI); the polyester polyol is 1,2-propanediol; the amino group chain extender is ethylene diamine; The ultraviolet light stabilizer is resorcinol monobenzoate; The heat stabilizer is dibasic lead phosphite. The solvent I is N,N-dimethylacetamide, and the solvent II is N,N-dimethylacetamide.

The specific method of spray coating the top coat is to add a certain amount of solvent, that is, N-N-dimethylacetamide, to the polyurethane/polyurea solution in which the two-dimensional material is composited, so that the bottom coat reaches the spray coating standard; Then spray coat it evenly over the primer using a spray gun.

Example 4:

The difference from Example 1 is that

In the degradation immune bionic protective coating layer, the primer is a self-healing epoxy powder obtained by uniformly dispersing GO-modified polyurea-based double-walled microcapsules and polydopamine in an epoxy resin, and the thickness at which the primer forms a film is 800 μm; The thickness at which the top coat forms a film is 300 μm.

The manufacturing method is as follows.

(1) Pre-treatment steps for the concrete surface:

(1a) Same as Example 1.

(1b) Same as Example 1.

(2) preparing a non-specific stress self-healing immune layer:

After completing the pre-treatment of the concrete in step (1), heating to 60 ° C., and then spray-coating the primer to obtain a non-specific stress self-restoring immune layer; The primer is an epoxy resin, and the manufacturing method is as follows,

(2a) Same as Example 1.

(2b) Same as Example 1.

(2c) preparing a self-healing epoxy powder; GO-modified polyurea-based double-walled microcapsules obtained in step (2a), polydopamine microspheres obtained in step (2b) and epoxy resin curing agent I were added to the powdery epoxy resin and uniformly dispersed. obtain an epoxy powder of restoration; The addition amount of the polydopamine microspheres was 0.5 wt% of the epoxy resin, and the addition amount of the GO-modified polyurea-based double-walled microcapsule was 6 wt% of the epoxy resin. Here, the model of the epoxy resin is E51. The epoxy resin curing agent I is dicyandiamide.

The specific method of spray coating the primer is to use a hot melt spray coating method, and in detail, add self-healing epoxy powder to a hot melt spray coater, heat it up to 200 ° C, and use a spray gun to concrete the concrete. spray coat evenly on the surface of

(3) Preparing a non-specific damage self-differentiation immune layer:

After completing the spray coating of the undercoat, the surface temperature is maintained at not lower than 30 ° C, and immediately proceeds with the spray coating of the topcoat to obtain a non-specific damage self-differentiation immune layer, thereby reducing the deterioration immune bionic protective coating layer. complete the manufacturing The top coat is a polyurethane / polyurea solution in which a two-dimensional material is combined, and the manufacturing method is as follows, uniformly mixing polyether, solvent I and emulsifier, vacuum dehydration at 100 ° C. for 3 h, and then, 35 Cool to °C, add isocyanate monomer slowly, and pre-polymerize for 15 min to obtain a free polymer. The two-dimensional material, ultraviolet light stabilizer, heat stabilizer, polyester polyol and amino group chain extender are added to solvent II, mixed uniformly, and then added to the pre-polymer, kept warm, and reacted for 1 h to make the two-dimensional material composite. A polyurethane/polyurea solution was obtained. The coating layer matrix of the top coat is a hybrid polyurethane-hybrid polyurea.

Here, the functional group equivalent ratio of the hydroxyl group and “hydroxyl group + amino group” of the polyester polyol-amino group chain extender is 0.75: 1, and the functional group equivalent ratio of -NCO and “hydroxyl group + amino group” in the reaction system is 1.1: 1, the amount of the two-dimensional material is 0.5wt% of the isocyanate monomer, the amount of the ultraviolet light stabilizer is 0.05wt% of the isocyanate monomer, and the amount of the heat stabilizer is 2wt% of the isocyanate monomer.

Here, the polyether is polyoxy propylene glycol; The two-dimensional material is montmorillonite; The isocyanate monomer is isophorone diisocyanate (IPDI); the polyester polyol is 1,6-hexanediol; The amino group chain extender is 1,6-diaminohexane; The ultraviolet light stabilizer is 2,4-dihydroxybenzophenone; The heat stabilizer is calcium stearate. The solvent I is N,N-dimethylacetamide, and the solvent II is N,N-dimethylacetamide.

The specific method of spray coating the top coat is to add a certain amount of solvent, that is, N-N-dimethylacetamide, to the polyurethane/polyurea solution in which the two-dimensional material is composited, so that the bottom coat reaches the spray coating standard; Then spray coat it evenly over the primer using a spray gun.

Example 5:

The difference from Example 1 is that

In the degradation immune bionic protective coating layer, the primer is a self-healing epoxy solution obtained by uniformly dispersing GO-modified polyurea-based double-walled microcapsules and polydopamine in an epoxy resin, and the thickness at which the primer forms a film is 250 μm; The thickness at which the top coat forms a film is 100 μm.

The manufacturing method is as follows.

(1) pre-treating the concrete surface:

(1a) Same as Example 1.

(1b) The concrete surface is immersed using a silane emulsion, the temperature of the concrete surface during the immersion period is 35 ° C, and the depth of immersion in the concrete is 3 mm. The silane emulsion is obtained by hydrolyzing silane monomers; The silane monomer is trimethoxyvinylsilane.

(2) preparing a non-specific stress self-healing immune layer:

After completing the pre-treatment of the concrete in step (1), heating to 35 ° C., and then spray-coating the primer to obtain a non-specific stress self-restoring immune layer; The primer is an epoxy resin, and the manufacturing method is as follows,

(2a) Same as Example 1.

(2b) preparing polydopamine microspheres; polydopamine was prepared by water oxidation method, stirring an ethanol solution and aqueous ammonia at a constant concentration at 40 ° C, adding a certain amount of dopamine hydrochloride solution, stirring and reacting for 10 h; After the reaction is complete, centrifugal washing is performed to obtain polydopamine microspheres.

(2c) preparing a self-healing epoxy solution; The GO-modified polyurea-based double-walled microcapsules obtained in step (2a) and the polydopamine microspheres obtained in step (2b) were added to an epoxy resin solution and dispersed at high speed to ensure uniform mixing of the system; After the dispersion is completed, the epoxy resin curing agent II is added and stirred uniformly to obtain a self-healing epoxy solution. The addition amount of the polydopamine microspheres was 6wt% of the epoxy resin, and the addition amount of the GO-modified polyurea-based double-walled microcapsules was 0.5wt% of the epoxy resin. Here, the model of the epoxy resin is E44. The epoxy resin curing agent II is a polyamide resin.

The specific method of spray coating the primer is to use the spray coating method of the solution, in detail, add a certain amount of solvent to the self-healing epoxy solution to make the primer reach the spray coating standard; Then, it is spray-coated uniformly on the concrete surface; The solvent is a mixed solution of xylene and 1-butanol.

(3) Preparing a non-specific damage self-differentiation immune layer:

After completing the spray coating of the undercoat, the surface temperature is maintained at not lower than 30 ° C, and immediately proceeds with the spray coating of the topcoat to obtain a non-specific damage self-differentiation immune layer, thereby reducing the deterioration immune bionic protective coating layer. complete the manufacturing The top coat is a polyurea solution in which two-dimensional materials are combined, and the manufacturing method is as follows, uniformly mixing polyether, solvent I and emulsifier, vacuum dehydration at 110 ° C for 1 h, and then cooling to 45 ° C , slowly adding the isocyanate monomer, and pre-polymerizing for 5 min to obtain a free polymer. The two-dimensional material, ultraviolet light stabilizer, heat stabilizer, polyester polyol and amino group chain extender are added to solvent II, mixed uniformly, and then added to the free polymer, kept warm, and reacted for 3 h to make the two-dimensional material composite. Obtain a polyurea solution. The coating layer matrix of the top coat is pure polyurea.

Here, the functional group equivalent ratio of the hydroxyl group of the polyester polyol-amino group chain extender and “hydroxyl group + amino group” is 0: 1, and the functional group equivalent ratio of -NCO and “hydroxyl group + amino group” in the reaction system is 1.2: 1, the amount of the two-dimensional material is 15wt% of the isocyanate monomer, the amount of the ultraviolet light stabilizer is 0.5wt% of the isocyanate monomer, and the amount of the heat stabilizer is 0.05wt% of the isocyanate monomer.

the polyether is D230; The two-dimensional material is boron nitride; the isocyanate monomer is toluene diisocyanate (TDI); the amino group chain extender is ethylene diamine; The ultraviolet light stabilizer is a monobenzoate of resorcinol; The heat stabilizer is dibasic lead phosphite. The solvent I is N,N-dimethylacetamide, and the solvent II is N,N-dimethylacetamide.

The specific method of spray coating the top coat is to add a certain amount of solvent, that is, N-N-dimethylacetamide, to the polyurethane/polyurea solution in which the two-dimensional material is composited, so that the bottom coat reaches the spray coating standard; Then spray coat it evenly over the primer using a spray gun.

Example 6:

The degradation immune bionic protective coating layer prepared in Examples 1 to 5 was detected through an adhesion test and an electrochemical test.

Electrochemical experiments: Necessary for electrochemical experiments using reinforced concrete without a coating layer, concrete coated with a general polyurea coating layer, and reinforced concrete having a bionic protective coating layer described in Examples 1 to 5, respectively. prepare a sample The size of the reinforced concrete block sample is 150 × 150 × 150 mm, the concrete level is C30, the thickness of the concrete protective layer is 68 mm, the anchor length of the reinforcing bar is 70 mm, the sample is cured for 28 d, The polyurea coating layer and the coating layers described in Examples 1 to 5 were painted, and at the same time, a blank group without a coating layer was prepared to proceed with comparison. The sample was immersed in a 3.5% NaCl solution for 3 months, a rebar was used as a working electrode, a Saturated Calomel Electrode was a reference electrode, and a titanium mesh is a three-electrode system of auxiliary electrodes, the measurement of potentiodynamic polarization is carried out, the scanning range is ±250 mV close to the open-circuit potential, and the scanning speed is 0.5 mV/s. The obtained data is processed using the tafel extrapolation method to obtain self corrosion potential and corrosion current density.

Adhesion test: The adhesion test of the coating layer is conducted based on the regulations of 《Adhesion test of color paint and varnish separation method》 (GB/T5210-2006) and 《Adhesion test method》 (ASTM-D-4541). A general polyurea coating layer (control) and the coating layers described in Examples 1 to 5 were applied to the cured concrete surface, respectively. Before proceeding with the experiment, select a smooth and defect-free surface as the test surface, clean the test surface and column sample with absolute ethanol, select acrylic acid adhesive to adhere the column sample to the test surface, leave it for 24 h, and test proceed with

The experimental results are as shown in Table 1.

Table 1 Test results of electrochemical experiments and adhesion experiments

As can be seen from the test results of the electrochemical experiment shown in Table 1, after immersion for 3 months, the reinforced concrete without a coating layer has a corrosion potential of -0.579V and the highest corrosion current density of 2.8 × 10 ^-6 A · cm ² , which explains that the steel is in an active corrosion state and has the highest corrosion rate. Reinforced concrete coated with a general polyurea coating layer moved the corrosion potential forward to -0.310V, and the corrosion current density was lowered to 3.3×10 ^-9 A·cm ² . However, the reinforced concrete specimens prepared in Examples 1 to 5 of the present application have a corrosion potential of -0.289 to -0.187 V and a corrosion current density of 2.8 × 10 ^-10 to 9.4 × 10 ^-13 A cm ² am. As can be seen from this, compared to the reinforcing bar without a coating layer, the reinforced concrete specimens prepared in Examples 1 to 5 of the present application have a forward shift in corrosion potential of 0.3 to 0.4 V, and a corrosion current density of 4 to 7 digits lower. This is because the general polyurea coating layer realized immunity against corrosion of reinforcing bars to a certain extent, but the degradation immune bionic protective coating layer described in this application blocks seawater to a greater extent, thereby realizing effective immunity against corrosion of reinforcing bars. , which has a smaller corrosion current density, delays the occurrence of corrosion, and better realizes protection for reinforced concrete.

As can be seen from the test results of the adhesion test described in Table 1, the concrete coating layers prepared in Examples 1 to 5 all improved the adhesive strength to some extent compared to the general polyurea coating layer. Here, since Examples 2 and 4 had a shallow immersion depth in silane, the adhesive strength between the primer and the concrete surface was relatively low, and destruction occurred at the interface between the primer and concrete, but the bond strength was still similar to that of general polyurea. higher than the coating layer. However, the thickness of the film formed in Example 5 was the thinnest and the thickness of the top coat was the thinnest, so the adhesive strength was the lowest, and destruction occurred at the point of the top coat with the thinnest film thickness. Since the silane immersion depth applied in Example 3 is the deepest and the solution-type primer can penetrate into the concrete, the bonding ability between the primer and the concrete interface is the strongest; Since the top coat with the thickest film thickness formed in Example 3 was used, the tensile ability was strong, so the undercoat reached its maximum strength during the experiment and fractured. It is explained that the adhesive strength of the agent is higher than that of the material itself and has excellent adhesion. In addition, in Examples 1 to 5, no destruction occurred at the interface between the primer and the top coat, and this is because the strength between the interface of the primer and the top coat using a network in which the interface interpenetrates is greater than the strength of the entire material. demonstrate that it is not low, and also prove that the two-layer structure has already been formed into an integral interfacial system.

Overall, the degradation immune bionic protective coating layer used in the repair process described in this application is composed of two layers, namely a primer and a top coat, but interpenetrates at the interface point to form a network interface where molecules crosslink and interpenetrate, so that the two are fused together The key point problem with weak interfaces has been solved. In addition, both the primer and the concrete surface of the immune interface are interconnected through chemical bonding to improve the interfacial adhesion between the interface system and the concrete. Therefore, the deterioration immune bionic protective coating layer described in this application solves the problem that the protective coating layer is easily damaged in the prior art, thereby restoring physical cracks and protecting concrete in two aspects of resisting chemical erosion, thereby providing important economic values and social effects. can be achieved

1: concrete
2: Primer
3: top coat
4: External water environment
5: Microcapsules of self-healing
6: coating layer matrix
7: Self-healing polymers
8: corrosive medium
9: 2D material
10: coating layer matrix

Claims (10)

In the manufacturing method of the deterioration immune bionic protective coating layer used in the repair process,
Include the steps below,
(1) pre-treating the concrete surface:
(1a) treating the concrete surface to make the concrete surface clean and flat to reach a certain surface roughness;
(1b) immersing the concrete surface with a silane emulsion, the temperature of the concrete surface during the immersion period is 5 to 40 ° C, and the depth of immersion in the concrete is 1 to 4 mm;
(2) preparing a non-specific stress self-healing immune layer:
After completing the pre-treatment of the concrete in step (1), heating to 25 to 60 ° C., and then spray-coating the primer to obtain a non-specific stress self-healing immune layer; The thickness at which the primer forms a film is 250 to 1000 μm; The primer is an epoxy resin, and the manufacturing method is as follows,
(2a) preparing GO-modified polyurea-based double-walled microcapsules;
(2b) preparing polydopamine microspheres;
(2c) preparing a self-healing epoxy powder or epoxy solution;
GO-modified polyurea-based double-walled microcapsules obtained in step (2a), polydopamine microspheres obtained in step (2b) and epoxy resin curing agent I were added to the powdery epoxy resin and uniformly dispersed. obtain an epoxy powder of restoration; Alternatively , the GO-modified polyurea-based double-walled microcapsules obtained in step (2a) and the polydopamine microspheres obtained in step (2b) were added to an epoxy resin solution and dispersed at high speed to ensure uniform mixing of the system, ; After the dispersion is completed, the epoxy resin curing agent II is added and stirred uniformly to obtain a self-healing epoxy solution; In the prepared self-healing epoxy powder or self-healing epoxy solution, the polydopamine microspheres and GO-modified polyurea-based double-walled microcapsules are added in an amount of 0.5 to 10 wt% of the epoxy resin;
(3) Preparing a non-specific damaged self-differentiation immune layer:
After completing the spray coating of the undercoat, the surface temperature is maintained at not lower than 30 ° C, and immediately proceeds with the spray coating of the topcoat to obtain a non-specific damage self-differentiation immune layer, thereby reducing the deterioration immune bionic protective coating layer. complete manufacturing; The thickness at which the top coat forms a film is 100 to 2000 μm; The top coat is a polyurethane/polyurea solution in which a two-dimensional material is combined, and the manufacturing method is as follows, uniformly mixing polyether, solvent I and emulsifier, and vacuuming at 100 to 120 ° C. for 1 to 3 h. dehydrated, then cooled to 20 to 65° C., slowly added an Isocyanate monomer, and pre-polymerized for 5 to 60 min to obtain a pre-polymer; Two-dimensional material, ultraviolet light stabilizer, heat stabilizer, polyester polyol and amino group chain extender are added to solvent II, mixed uniformly, and then added to the pre-polymer again, and warmed to 0.5 to 3 h to obtain a polyurethane/polyurea solution in which two-dimensional materials are composited; Method for producing a degradation immune bionic protective coating layer used in a repair process, characterized in that the coating layer matrix of the top coat is pure polyurethane, hybrid polyurethane-hybrid polyurea or pure polyurea. According to claim 1,
The equivalence ratio of the hydroxyl group of the polyester polyol-amino group chain extender described in step (3) and the functional group of “hydroxyl group + amino group” is (0-0.37): 1 and (0.48- 1): 1, and the functional group equivalent ratio of -NCO and "hydroxyl group + amino group" in the reaction system is (1.05-1.2): 1, and the amount of the two-dimensional material is 0.5 to 15 wt% of the isocyanate monomer, and the The amount of the ultraviolet light stabilizer is 0.01 to 1 wt% of the isocyanate monomer, and the amount of the heat stabilizer is 0.05 to 5 wt% of the isocyanate monomer. According to claim 2,
In the coating layer matrix of the top coat described in step (3), when polyurethane is used as the main material, the polyether used is polyether polyalcohol; When polyurea is used as a main material, the polyether used is a polyether amine (polyether amine), characterized in that the manufacturing method of the degradation immune bionic protective coating layer used in the repair process. According to claim 3,
The silane emulsion described in step (1b) above is obtained through hydrolysis of silane monomers; The silane monomer is triethoxyvinylsilane, trimethoxyvinylsilane, triethoxymethylsilane, triethoxyoctylsilane, triethoxyisobutylsilane A method for producing a deterioration immune bionic protective coating layer used in a repair process, characterized in that one or more. According to claim 3,
The method for preparing the polydopamine microspare described in step (2b) is as follows, specifically, polydopamine is prepared using an aqueous phase oxidation method, and an ethanol solution of a certain concentration and ammonia water are prepared at 40 to 50 ° C. Stirring, adding a certain amount of dopamine hydrochloride solution, stirring and reacting for 8 to 10 h; After the reaction is completed, a method for producing a degraded immune bionic protective coating layer used in a repair process, characterized in that to obtain a polydopamine microspare by centrifugation. According to claim 3,
The model of the epoxy resin described in step (2c) is E-44, E51 or E-54; The epoxy resin curing agent I is one of dicyandiamide, dicyandiamide derivative, acid anhydride, imidazole, cyclic ether and phenolic resin, or several; The epoxy resin curing agent II is a polyamide resin, ethylene diamine, diethylenetriamine, tetraethylenepentamine, maleic anhydride and phthalic anhydride A method for producing a deterioration immune bionic protective coating layer used in a repair process, characterized in that one or more of them. According to claim 3,
The specific method of spray coating the primer described in step (2) is,
(1) Using the hot melt spray coating method, in detail, adding self-healing epoxy powder to the hot melt spray coating machine, heating it to 140 to 200 ° C, and using a spray gun to coat the concrete. Spray coating uniformly on the surface;
or (2) use the method of spray coating or brush coating of the solution, specifically, add a certain amount of solvent to the self-healing epoxy solution to make the primer reach the spray coating standard; Then, it is spray-coated or brush-coated uniformly on the concrete surface; The method of manufacturing a deterioration immune bionic protective coating layer used in a repair process, characterized in that the solvent is xylene, 1-butanol or a mixed solution of both. According to claim 3,
The polyether polyalcohol described in step (3) is polyoxy propylene glycol, trihydroxymethylpropane polyether, polytetrahydrofuran glycol, tetrahydrofuran oxide- one or more of propylene copolymer glycol (tetrahydrofuranoxide propylene copolymer glycol) and polyoxyethylene glycol;
the polyether amine is one or more of D230, D400, D2000, T403, T5000;
The two-dimensional material is one or more of graphene, mica, montmorillonite, graphite, and boron nitride;
The isocyanate monomer is hexamethylene diisocyanate, dicyclohexylmethane diisocyanate, methylene diphenyl diisocyanate, toluene diisocyanate and isophorone diisocyanate. one or several isophorone diisocyanates;
The polyester polyol is ethylene glycol, diethylene glycol, 1,2-propanediol, dipropylene glycol, 1,4-butanediol (1,2-propanediol) 4-butanediol), neopentyl glycol, 1,6-hexanediol, adipic acid, trihydroxymethylpropane and isophthalic acid ) is one or more;
The amino group chain extender is diethyl toluene diamine, dimethyl thio toluene diamine, N, N'-dialkyl methyl diphenylamine, cyclo Cyclohexanediamine, MDH chloride, ethylene diamine, 1,3-diaminopropane, 1,4-diaminobutane, diethylenetriamine (diethylenetriamine), pentaethylene hexamine, hexaethylene diamine, tetraethylenepentamine, 1,6-diaminohexane and 3,3'-4 one or more of ,4'-diamino-diphenyl methane;
The UV light stabilizer includes phenyl salicylate, salicylic acid-4-octylphenyl ester, resorcinol monobenzoate, 2-hydroxy-4- 2-hydroxy-4-methoxybenzophenone, 2,4-dihydroxybenzophenone and 2-hydroxy-4-octyloxy benzophenone benzophenone), one or more;
The heat stabilizer is tribasic lead sulfate, dibasic lead phosphite, dibasic lead stearate, cadmium stearate, barium stearate, calcium stearate, stearic acid A method for producing a deterioration immune bionic protective coating layer used in a repair process, characterized in that it is one or more of lead stearate, zinc stearate, fatty acid salt and maleate. According to claim 3,
A specific method of spray coating the top coat,
A certain amount of solvent, that is, NN-Dimethylacetamide, is added to the polyurethane/polyurea solution in which the two-dimensional material obtained in step (3) is combined so that the primer reaches the spray coating standard; Then, a method for producing a deterioration immune bionic protective coating layer used in a repair process, characterized in that it is spray-coated uniformly on the primer using a spray gun. In the degradation immune bionic protective coating layer used in the repair process manufactured by the method according to claims 1 to 9,
The degradation immune bionic protective coating layer is a protective coating layer of the concrete matrix,
The degradation immune bionic protective coating layer is composed of two layers, that is, a primer and a top coat; interdiffusion between the two layers and chemical crosslinking occurs, molecules are crosslinked to form an interpenetrating network; The primer is a self-healing epoxy powder or a self-restoring epoxy solution obtained by uniformly dispersing GO-modified polyurea-based double-walled microcapsules and polydopamine in an epoxy resin, and the primer has a thickness for forming a film. 250 to 1000 μm; The top coat is a polyurethane / polyurea solution in which a two-dimensional material is combined, and the top coat has a thickness of 100 to 2000 μm to form a film.

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