CN112694824B - Deteriorated immune bionic protective coating for steel structure engineering and preparation method thereof - Google Patents

Deteriorated immune bionic protective coating for steel structure engineering and preparation method thereof Download PDF

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CN112694824B
CN112694824B CN202011577827.0A CN202011577827A CN112694824B CN 112694824 B CN112694824 B CN 112694824B CN 202011577827 A CN202011577827 A CN 202011577827A CN 112694824 B CN112694824 B CN 112694824B
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polyurea
steel structure
immune
primer
protective coating
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CN112694824A (en
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马衍轩
刘加童
葛亚杰
张鹏
吴睿
宋晓辉
薛善彬
崔祎菲
鲍久文
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Qingdao University of Technology
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Priority to KR1020237000304A priority patent/KR102516293B1/en
Priority to PCT/CN2021/087333 priority patent/WO2022141950A1/en
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Abstract

The invention discloses a deteriorated immune bionic protective coating for steel structure engineering and a preparation method thereof. The deteriorated immune bionic protective coating is a protective coating on a steel structure substrate and sequentially consists of three layers of primer, intermediate paint and finish paint from inside to outside; and the two adjacent layers are mutually diffused and chemically cross-linked to form a molecular cross-linked interpenetrating network. The primer is a corrosion inhibitor-polyurethane blending system, and the thickness of the primer film is 80-150 mu m. The intermediate paint is a self-repairing polyurea blending solution obtained by uniformly dispersing GO modified polyurea-based double-wall microcapsules and polydopamine in a polyurethane-polyurea elastomer, and the thickness of the intermediate paint film is 100-400 mu m. The finish paint is a two-dimensional material composite polyurethane/polyurea solution, and the film forming thickness of the finish paint is 150-500 mu m. The deteriorated immune bionic protective coating simulates a three-defense line structure of a human immune system, protects a steel structure from two aspects of physical crack repair and chemical corrosion resistance, and realizes immunity to steel structure deterioration.

Description

Deteriorated immune bionic protective coating for steel structure engineering and preparation method thereof
Technical Field
The invention belongs to the field of materials, relates to a protective coating and a preparation method thereof, and particularly relates to a steel structure engineering structure degradation immune bionic protective coating system and a preparation method thereof.
Background
The steel structure is one of the main building structure types, and the structure mainly comprises steel beams, steel columns, steel trusses and other members made of section steel, steel plates and the like, and rust removing and preventing processes such as silanization, pure manganese phosphating, washing drying, galvanization and the like are adopted. The components or parts of the steel structure are typically joined by welds, bolts or rivets. Because the steel structure has light dead weight and simple and convenient construction, the steel structure is widely applied to the construction field of large-scale factory buildings, venues and super high-rise buildings at present. The size of the steel structure building marks the economic strength and the economic development degree of a country or a region. With the remarkable increase of national economy and remarkable strengthening of national strength in China, the steel yield becomes a world large country, the active and reasonable use of steel in construction is provided, and steel structure buildings are gradually increased in economically developed areas. Particularly, under the promotion of the Olympic Games in 2008, China builds a large number of steel structure venues, airports, stations and high-rise buildings, wherein the steel structure buildings with the top-grade level in the world, such as the national stadium of the Olympic Games, and the like.
However, steel structures are susceptible to corrosion and care must be taken to protect, particularly thin-walled components, and therefore buildings which are in a more corrosive medium are not amenable to steel structures. Generally, the steel structure needs to be derusted, galvanized or painted, and needs to be maintained regularly. The rust of the steel structure is thoroughly removed before being painted with the paint, the newly built steel structure is generally brushed again at certain intervals, and the maintenance cost is high. Various high-performance coatings and weathering resistant steel which is not easy to rust are developed at home and abroad, and the problem of poor rust resistance of a steel structure is expected to be solved. The current common steel structure coating protection technology is also used; good protection of the steel structure is always provided as long as the coating adheres to the steel structure substrate without failure damage. The steel structure coating protection can be carried out in a full-stage protection mode from the delivery, transportation to service of the component, and has the characteristic of full-life-cycle protection. However, in practical application, the steel structure coating protection technology is difficult to realize the full life cycle protection. This is because: (1) the interface bonding force of the coating/steel structure is weak, and debonding is easy to occur under the action of external load; (2) the existing steel structure coating protection is mostly an epoxy coating which has high hardness and brittleness; when the coating is processed on a construction site, the coating is easy to damage; in other words, the existing coating protection technology cannot compromise mechanical properties and processability. For the coating protection technology, once the coating is locally damaged, the local pitting phenomenon of a component can be caused, so that the whole coating protection system can be failed; (3) the existing coating protection technology can only provide anti-corrosion protection by isolating a steel structure matrix, but cannot give consideration to repair and immunity of cracks and erosion factors.
Disclosure of Invention
Aiming at the problems of the existing steel structure coating protection technology, the invention discloses a degraded immune bionic protection coating for steel structure engineering. The degraded immune bionic protective coating simulates three defense lines of a human immune system, adopts a structure system of separation-resistance-slow and realizes the bionic immune antiseptic treatment of a steel structure through the optimized design of the structure of the steel structure coating.
The technical scheme of the invention is as follows:
the preparation method of the deteriorated immune bionic protective coating for the steel structure engineering comprises the following steps:
(1) preparing a specific targeting controlled-release corrosion inhibition immune layer:
(1a) and (2) treating the surface of the steel, removing floating dust, welding spatters, grease and other pollutants on the surface of the steel structure, removing oxides, rust, coatings and the like on the surface of the steel by adopting a shot blasting or sand blasting mode after the treatment is finished, and enabling the surface of the steel to have certain roughness to obtain the preliminarily treated steel structural member I. The surface treatment is in accordance with visual assessment of surface cleanliness of steel surface treatment before coating (GB/T8923). The surface of the treated steel needs to be sprayed with the primer within 24 hours, and if the surface of the steel is rusted and polluted before spraying, the surface treatment needs to be carried out again.
(1b) Preparing a silane coupling agent solution, immersing the steel structural member I in the silane coupling agent solution for 5-10 minutes, taking out the steel structural member I, and curing the steel structural member I at the temperature of 100-150 ℃ for 1-3 hours to obtain a treated steel structural member II; the concentration of the silane coupling agent solution is 0.5-1.0%, and the silane coupling agent is KH-550, KH-560 or KH-570; the silane coupling agent solution is prepared by adopting the following method: mixing a silane coupling agent and an alcohol-water mixture, adjusting the pH value to 3.5-5.5 according to the type of the coupling agent, and standing and hydrolyzing for 24-48 h.
(1c) Immediately coating a primer on the surface of the steel structural member II to form a film, and then carrying out primary curing for 0.5-2h at 55-60 ℃ to obtain a specific targeted controlled-release corrosion inhibition immune layer; the thickness of the primer film is 80-150 μm, and the primer is a corrosion inhibitor-polyurethane blending system; the corrosion inhibitor is compounded by polyaspartic acid and one or more of polyphosphate, molybdate and organic phosphorus corrosion inhibitor. The polyaspartic acid corrosion inhibitor is compounded with other corrosion inhibitors, so that the corrosion inhibitor has the characteristic of environmental protection, when the primer is damaged, the corrosion inhibitor in the matrix can be released and tightly adsorbed on the surface of a bare steel structure, the corrosion of corrosive ions to the steel structure member is blocked, and the targeted controlled release immunity of the primer to corrosive factors is realized.
The primer is prepared by the following method: carrying out vacuum dehydration on polyoxypropylene diol at the temperature of 100-120 ℃ for 1-3h, cooling to 40-60 ℃, and slowly adding an isocyanate monomer; after the isocyanate monomer is completely added, heating to 65-80 ℃, adding acetone for multiple times during the heating to reduce the viscosity, and reacting for 1-2 hours to obtain a prepolymer; uniformly mixing the corrosion inhibitor and the polyhydric alcohol according to a certain proportion, adding the mixture into the prepolymer, cooling to 40-50 ℃, reacting for 1h, continuously cooling to room temperature, and adding water for emulsification; finally, vacuum evaporating acetone to obtain the corrosion inhibitor-polyurethane blending system.
The key of the step is as follows: the priming paint is brushed immediately after the surface of the steel structure is treated, and no macroscopic dirt and oxidation phenomenon can be caused on the surface of the steel structure; thereby ensuring that the primer is connected with the steel structure through chemical bonds. The principle is as follows: hydroxyl generated by the oxidation of the surface of the steel structure and a hydrolysate of the coupling agent form a hydrogen bond, and then partial dehydration is carried out to form a covalent bond; similarly, the coupling agent and the surface of the primer form a covalent bond, and the primer and the steel structure form a chemical bond connection through the coupling agent.
(2) Preparing a non-specific self-repairing stress immune layer: after the primer in the step (1) is cured, heating to 80-100 ℃, and immediately spraying intermediate paint toEnsuring that the molecules between the two layers can undergo osmotic exchangeAnd obtaining the nonspecific self-repairing stress immune layer. The thickness of the intermediate paint film is 100-400 mu m; the intermediate paint is a self-repairing polyurea solution, and the preparation method comprises the following steps:
(2a) preparing GO modified polyurea-based double-wall microcapsules; the graphene oxide modified polyurea-based double-wall microcapsule is prepared by a preparation method disclosed by GO-modified double-walled polyurea microcapsules/epoxy compositions for mineral inorganic self-sealing coating (Materials & Design, Ma Y, Zhang Y, Liu J, et al 2020,189: 108547).
(2b) Preparing polydopamine microspheres; preparing polydopamine by adopting a water phase oxidation method, stirring an ethanol solution with a certain concentration and ammonia water at 40-50 ℃, adding a certain amount of dopamine hydrochloride solution, and stirring and reacting for 8-10 hours; and centrifuging and washing after the reaction is finished to obtain the polydopamine microsphere.
(2c) Preparing a self-repairing polyurea solution: adding polyether amine into a solvent, uniformly stirring, slowly dripping into isocyanate, controlling the reaction temperature to be 0-30 ℃, and pre-polymerizing after drippingObtaining prepolymer in 0.5-1 h; adding the polydopamine microspheres obtained in the step (2b) and an amino chain extender into a solvent, uniformly mixing, adding the mixture into the prepolymer, and controlling-NCO and NH in a reaction system2The molar ratio of the poly (dopamine)/polyurea elastomer is 1.05:1-1.2:1, and the reaction lasts for 5-10 min to obtain the poly (dopamine)/polyurea elastomer; adding the GO modified polyurea-based double-wall microcapsule obtained in the step (2a) into a polydopamine/polyurea elastomer, and stirring at a high speed to uniformly disperse the GO modified polyurea-based double-wall microcapsule in the polydopamine/polyurea elastomer to obtain a self-repairing polyurea solution. The self-repairing polyurea solution combines an external self-repairing double-wall microcapsule with an intrinsic self-repairing means, so that the microcapsule at the damaged part can release a repairing agent to repair the damage, and hydrogen bonds formed among polydopamine molecules can repair cavities left after the microcapsule is released and damaged parts of the microcapsule which are not triggered, thereby further improving the self-repairing efficiency of the intermediate coat.
Wherein the polyether amine is one or more of D230, D400 and D2000, and the isocyanate is one or more of Hexamethylene Diisocyanate (HDI), dicyclohexylmethane diisocyanate (HMDI), diphenylmethane diisocyanate (MDI), Toluene Diisocyanate (TDI) and isophorone diisocyanate (IPDI); the amino chain extender is one or more of diethyl toluene diamine, dimethyl sulfur toluene diamine, N ' -dialkyl methyl diphenylamine, cyclohexane diamine, chlorinated MDH, ethylene diamine, 1, 3-diaminopropane, 1, 4-diaminobutane, diethylene triamine, pentaethylene hexamine, hexaethylene diamine, tetraethylene pentamine, 1, 6-hexamethylene diamine and 3,3' -4,4' -diamino-diphenylmethane.
The intermediate paint spraying method comprises the following specific steps: adding a certain amount of solvent N, N-dimethylacetamide into the self-repairing polyurea solution obtained in the step (2c) to enable the intermediate paint to reach the spraying standard; then the paint is evenly sprayed on the primer by a spray gun. The primarily cured primer and the chain segment of the spraying self-repairing polyurea mutually permeate at the interface to form a molecular mutual transmission network.
(3) Preparation of non-specific lesion self-differentiating immune layer: and after the spraying of the primer is finished, keeping the surface temperature not lower than 30 ℃, and immediately spraying the finish to obtain a nonspecific damage self-differentiation immune layer, thereby finishing the preparation of the degraded immune bionic protective coating. The film forming thickness of the finish paint is 150-500 mu m; the finish paint is a two-dimensional material composite polyurethane/polyurea solution, and the preparation method comprises the following steps: polyether, solvent I and emulsifier are mixed evenly, vacuum dehydration is carried out for 1-3h at the temperature of 100-120 ℃, then cooling is carried out to 20-65 ℃, isocyanate monomer is slowly added, and prepolymerization is carried out for 5-60min to obtain prepolymer. Adding the two-dimensional material, the ultraviolet light stabilizer, the heat stabilizer, the polyester polyol and the amino chain extender into the solvent II, uniformly mixing, adding into the prepolymer, and reacting for 0.5-3h under heat preservation to obtain the two-dimensional material composite polyurethane/polyurea solution. The coating matrix of the finish paint is pure polyurethane, semi-polyurethane semi-polyurea or pure polyurea. When the coating substrate takes polyurethane as a main body, the polyether used is polyether polyol; when polyurea is used as the main component, the polyether used is polyether amine. The two-dimensional material in the finish paint is distributed in a layered manner, so that the invasion path of a corrosive medium can be blocked or prolonged, the durability of the protected concrete material is improved, and the light and heat stabilizers in the finish paint can improve the aging resistance of the coating.
The equivalent ratio of hydroxyl groups of the polyester polyol-amino chain extender to functional groups of hydroxyl groups and amino groups is (0-0.37):1 and (0.48-1):1, the equivalent ratio of the functional groups of NCO and hydroxyl groups and amino groups in the reaction system is (1.05-1.2):1, the using amount of the two-dimensional material is 0.5-15 wt% of isocyanate monomers, the using amount of the ultraviolet light stabilizer is 0.01-1wt% of the isocyanate monomers, and the using amount of the heat stabilizer is 0.05-5wt% of the isocyanate monomers.
Wherein, the polyether polyol is one or more of polyoxypropylene diol, trimethylolpropane polyether, polytetrahydrofuran diol, tetrahydrofuran-oxypropylene copolymerization diol and polyoxyethylene diol; 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 one or more of Hexamethylene Diisocyanate (HDI), dicyclohexylmethane diisocyanate (HMDI), diphenylmethane diisocyanate (MDI), Toluene Diisocyanate (TDI) and isophorone diisocyanate (IPDI); the polyester polyol is one or more of ethylene glycol, diethylene glycol, 1, 2-propylene glycol, dipropylene glycol, 1, 4-butanediol, neopentyl glycol, 1, 6-hexanediol, adipic acid, trimethylolpropane and isophthalic acid; the amino chain extender is one or more of diethyl toluene diamine, dimethyl sulfur toluene diamine, N ' -dialkyl methyl diphenylamine, cyclohexane diamine, chlorinated MDH, ethylene diamine, 1, 3-diaminopropane, 1, 4-diaminobutane, diethylene triamine, pentaethylene hexamine, hexaethylene diamine, tetraethylene pentamine, 1, 6-hexamethylene diamine and 3,3' -4,4' -diamino-diphenylmethane; the ultraviolet light stabilizer is one or more of phenyl salicylate, salicylic acid-4-octylphenyl ester, resorcinol monobenzoate, 2-hydroxy-4-methoxybenzophenone, 2, 4-dihydroxybenzophenone and 2-hydroxy-4-n-octyloxybenzophenone; the heat stabilizer is one or more of tribasic lead sulfate, dibasic lead phosphite, dibasic lead stearate, cadmium stearate, barium stearate, calcium stearate, lead stearate, zinc stearate, fatty acid salt and maleate.
The specific method for spraying the finish paint comprises the following steps: adding a certain amount of solvent N, N-dimethylacetamide into the two-dimensional material composite polyurethane/polyurea solution to enable the primer to reach the spraying standard; then the paint is evenly sprayed on the primer by a spray gun.
The deteriorated immune bionic protective coating for the steel structure engineering is prepared by the method, and is a protective coating on a steel structure substrate. The deteriorated immune bionic protective coating consists of three layers of primer, intermediate paint and finish paint from inside to outside in sequence; and the two adjacent layers are mutually diffused and chemically cross-linked to form a molecular cross-linked interpenetrating network. The primer isCorrosion inhibitor-polyurethaneThe corrosion inhibitor is a mixture of polyaspartic acid and one or more of polyphosphate, molybdate, an organic phosphorus corrosion inhibitor, aluminum powder and zinc powder, and the thickness of the formed primer film is 80-150 mu m. The intermediate paint is a GO modified polyurea-based double-wall microcapsule and polydopamine in-polyThe polyurethane-polyurea elastomer is uniformly dispersed to obtain the self-repairing polyurea blending solution, and the thickness of the intermediate paint film is 100-400 mu m. The finish paint is a two-dimensional material composite polyurethane/polyurea solution, and the film forming thickness of the finish paint is 150-500 mu m.
The preparation principle is as follows: the primer, the intermediate paint and the finish paint are sequentially coated on the steel structural member when the curing is not completely carried out, so that the two layers of paint at the interface are mutually diffused along with the solvent, and the long chains and the short chains of the polymer molecules are mutually permeated, diffused and wound to form an interpenetrating network. Wherein, the unreacted-NCO in chain segments and the hydroxyl or amino in the chain extender which are mutually diffused among the interfaces of the primer and the intermediate paint, the intermediate paint and the finishing paint can continuously react with the unreacted hydroxyl or amino in the chain extender and the-NCO in the chain segments of the opposite side, so that the three-layer paint surface is subjected to chemical crosslinking, and finally, the molecular crosslinking interpenetrating network is obtained by curing. Thus, essentially, the three-layer structure of the degraded immunobiomimetic protective coating is already substantially inseparable, forming one layer. In addition, the surface of the steel structure is treated by adopting a silane coupling agent, hydroxyl generated by oxidation of the surface of the steel structure forms a hydrogen bond with a hydrolysate of the coupling agent, then partial dehydration is carried out to form a covalent bond, and amino, epoxy or unsaturated double bond in the other end of the coupling agent can participate in the curing reaction of the primer, so that the surface of the steel structure is connected with the primer through a chemical bond, and the interfacial cohesion is further improved.
The invention has the beneficial effects that:
(1) the deteriorated immune bionic protective coating for steel structure engineering simulates a three-defense line structure of a human immune system, protects a steel structure from two aspects of physical crack repair and chemical corrosion resistance, realizes immunity to steel structure deterioration, overcomes the defects that the protective coating is easy to damage and can not be repaired in the prior art, and has important economic value and social benefit.
(2) The deteriorated immune bionic protective coating for steel structure engineering consists of three layers of priming paint, intermediate paint and finish paint from inside to outside in sequence, and not only adjacent two layers are mutually permeated at an interface to formCross-linked interpenetrating network boundary The three defense lines are integrated into a whole,the problems of interface weakness and the like do not exist.
(3) The degraded immune bionic protective coating for steel structure engineering provided by the invention has the advantages that the interface of the primer and the steel structure is treated by adopting a coupling agent, so that the primer and the steel structure are treatedThe primer is connected with the surface of the steel structure in a chemical bond modeThe binding force between the paint surface and the steel structure is enhanced.
Drawings
FIG. 1 is one of the structural schematic diagrams of the deteriorated immune bionic protective coating.
FIG. 2 is a schematic structural diagram of a primer in the degraded immune biomimetic protective coating according to the present invention;
FIG. 3 is a schematic structural diagram of a lacquer in the degraded immune-biomimetic protective coating according to the present invention;
FIG. 4 is a schematic structural diagram of a finish in the degraded immune biomimetic protective coating of the present invention;
wherein: 1: finishing paint; 2: intermediate paint; 3: priming paint; 4: steel material; 5: etching the medium; 6: a corrosion inhibitor; 7: a primer coated substrate; 8: self-repairing microcapsules; 9: coating the substrate with intermediate paint; 10: a self-healing polymer; 11: etching the medium; 12: a two-dimensional material; 13: and (3) coating a substrate with finish paint.
Detailed Description
The present invention will be further described with reference to the following examples.
Example 1:
the invention relates to a deteriorated immune bionic protective coating for ocean engineering, which is a protective coating on a steel structure substrate. The deteriorated immune bionic protective coating consists of three layers of primer, intermediate paint and finish paint from inside to outside in sequence; and the two adjacent layers mutually diffuse and are chemically crosslinked to form a molecular crosslinking interpenetrating network; the primer is a corrosion inhibitor-polyurethane blending system, and the thickness of the primer film is 100 mu m; the intermediate paint is a self-repairing polyurea solution, and the thickness of the formed film of the intermediate paint is 250 micrometers; the finish paint is a two-dimensional material composite polyurethane/polyurea solution, and the film forming thickness of the finish paint is 350 mu m. The preparation method comprises the following steps:
(1) preparation of specific targeting controlled-release corrosion-inhibition immune layer primer
Selecting Q345 steel, firstly treating the surface of the steel, removing floating dust, welding spatters, grease and other dirt on the surface of the steel structure, and after the treatment is finished, removing oxides, rust, coatings and the like on the surface of the steel by adopting a shot blasting or sand blasting mode, and enabling the surface of the steel to have certain roughness. The surface treatment is in accordance with visual assessment of surface cleanliness of steel surface treatment before coating (GB/T8923).
Mixing a silane coupling agent KH-560 with an alcohol-water mixture to prepare a dilute solution with the concentration of 0.5%, adjusting the pH value to 4.5, and standing for hydrolysis for 48 h. And (3) soaking the preliminarily treated steel structural member I in a silane coupling agent treatment solution for 10min, taking out, and curing at 100 ℃ for 1 hour to obtain a treated steel structural member II. Immediately brushing primer on the surface of the steel structural member II, and then carrying out primary curing for 1h at 55 ℃ to obtain a specific targeted controlled-release corrosion-inhibition immune layer (as shown in figure 2). The primer is prepared by the following method:
carrying out vacuum dehydration on polyoxypropylene glycol at 105 ℃ for 1h, cooling to 40 ℃, and slowly adding 2, 4-toluene diisocyanate monomer; after the isocyanate monomer is completely added, heating to 65 ℃, adding acetone for multiple times during the heating to reduce the viscosity, and reacting for 1.5 hours to obtain a prepolymer; uniformly mixing the corrosion inhibitor and the polyhydric alcohol according to a certain proportion, adding the mixture into the prepolymer, cooling to 45 ℃, reacting for 1h, continuously cooling to room temperature, and adding water for emulsification; finally, vacuum evaporating acetone to obtain the corrosion inhibitor-polyurethane blending system.
(2) Preparation of non-specific self-repairing stress immune layer intermediate paint
After the primer in the step (1) is cured, heating to 80 ℃, and immediately spraying intermediate paint toEnsuring molecules between two layers Osmotic exchange can occurAnd obtaining the nonspecific self-repairing stress immune layer (as shown in figure 3). The intermediate paint is a self-repairing polyurea solution, and the preparation method comprises the following steps:
(2a) preparing GO modified polyurea-based double-wall microcapsules; the graphene oxide modified polyurea-based double-wall microcapsule is prepared by a preparation method disclosed by GO-modified double-walled polyurea microcapsules/epoxy compositions for mineral inorganic self-sealing coating (Materials & Design, Ma Y, Zhang Y, Liu J, et al 2020,189: 108547).
(2b) Preparing polydopamine microspheres; preparing polydopamine by adopting a water phase oxidation method, mixing a 30% ethanol solution and 28% ammonia water according to a volume ratio of 45:1, stirring at 45 ℃, adding 10.5g of a 4.8% dopamine hydrochloride aqueous solution, and stirring for reacting for 10 hours; and centrifuging and washing after the reaction is finished to obtain the polydopamine microsphere.
(2c) Preparing a self-repairing polyurea solution: adding polyether amine into a solvent, uniformly stirring, slowly dripping into isocyanate, controlling the reaction temperature to be 20 ℃, and carrying out prepolymerization for 0.5h after dripping is finished to obtain a prepolymer; adding the polydopamine microspheres obtained in the step (2b) and an amino chain extender into a solvent, uniformly mixing, adding the mixture into the prepolymer, and controlling-NCO and NH in a reaction system2The molar ratio of the poly (dopamine)/polyurea elastomer is 1.05:1, and the reaction is carried out for 5min to obtain the poly (dopamine)/polyurea elastomer; adding the GO modified polyurea-based double-wall microcapsule obtained in the step (2a) into a polydopamine/polyurea elastomer, and stirring at a high speed to uniformly disperse the GO modified polyurea-based double-wall microcapsule in the polydopamine/polyurea elastomer to obtain a self-repairing polyurea solution.
Wherein the polyether amine is D230, and the isocyanate is isophorone diisocyanate (IPDI); the amine chain extender is ethylenediamine.
The intermediate paint spraying method comprises the following specific steps: adding a certain amount of solvent N, N-dimethylacetamide into the self-repairing polyurea solution obtained in the step (2c) to enable the intermediate paint to reach the spraying standard; then the paint is evenly sprayed on the primer by a spray gun.
(3) Preparation of non-specific lesion self-differentiating immune layer: and after the spraying of the primer is finished, keeping the surface temperature not lower than 30 ℃, and immediately spraying the finish to obtain a nonspecific damage self-differentiation immune layer, thereby finishing the preparation of the degraded immune bionic protective coating. The finish paint is two-dimensional material composite polyurethane, and the preparation method comprises the following steps: and (2) uniformly mixing the polyether, the solvent I and the emulsifier, dehydrating for 2 hours in vacuum at 105 ℃, then cooling to 55 ℃, slowly adding an isocyanate monomer, and carrying out prepolymerization for 5min to obtain a prepolymer. Adding the two-dimensional material, the ultraviolet light stabilizer, the heat stabilizer, the polyester polyol and the amino chain extender into the solvent II, uniformly mixing, adding into the prepolymer, and reacting for 2 hours under heat preservation to obtain the two-dimensional material composite polyurethane/polyurea solution. The coating matrix of the finish paint is pure polyurethane.
The equivalent ratio of hydroxyl of the polyester polyol-amino chain extender to functional groups of hydroxyl and amino is 1:1, the equivalent ratio of functional groups of NCO and hydroxyl and amino in the reaction system is 1.05:1, the using amount of the two-dimensional material is 1wt% of isocyanate monomer, the using amount of the ultraviolet light stabilizer is 0.1 wt% of isocyanate monomer, and the using amount of the heat stabilizer is 0.5 wt% of isocyanate monomer.
Wherein the polyether polyol is a polyoxypropylene diol; the two-dimensional material is graphene; the isocyanate monomer is Hexamethylene Diisocyanate (HDI); the polyester polyol is ethylene glycol; the amino chain extender is 1, 6-hexamethylene diamine; the ultraviolet light stabilizer is phenyl salicylate; 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 for spraying the finish paint comprises the following steps: adding a certain amount of solvent N, N-dimethylacetamide into the two-dimensional material composite polyurethane solution to enable the primer to reach the spraying standard; then the paint is evenly sprayed on the primer by a spray gun.
Example 2: in contrast to the embodiment 1, the process of the invention,
in the degraded immune bionic protective coating, the thickness of the formed film of the primer is 80 μm; the thickness of the intermediate paint film is 300 mu m; the thickness of the finish paint film is 150 mu m. The preparation method comprises the following steps:
(1) preparation of specific targeting controlled-release corrosion-inhibition immune layer primer
Mixing a silane coupling agent KH-550 with an alcohol-water mixture to prepare a diluted solution with the concentration of 1%, adjusting the pH value to 4, and standing for hydrolysis for 24 hours. And (3) soaking the preliminarily treated steel structural member I in a silane coupling agent treatment solution for 5min, taking out, and curing at 120 ℃ for 1 hour to obtain a treated steel structural member II. Immediately brushing primer on the surface of the steel structural member II, and then carrying out primary curing for 0.5h at 60 ℃ to obtain a specific targeted controlled-release corrosion-inhibition immune layer (as shown in figure 2). The primer is prepared by the following method:
carrying out vacuum dehydration on polyoxypropylene glycol at 105 ℃ for 1h, cooling to 40 ℃, and slowly adding 2, 4-toluene diisocyanate monomer; after the isocyanate monomer is completely added, heating to 65 ℃, adding acetone for multiple times during the heating to reduce the viscosity, and reacting for 1.5 hours to obtain a prepolymer; uniformly mixing the corrosion inhibitor and the polyhydric alcohol according to a certain proportion, adding the mixture into the prepolymer, cooling to 45 ℃, reacting for 1h, continuously cooling to room temperature, and adding water for emulsification; finally, vacuum evaporating acetone to obtain the corrosion inhibitor-polyurethane blending system.
(2) Preparation of non-specific self-repairing stress immune layer intermediate paint
After the primer in the step (1) is cured, the temperature is raised to 80 ℃, and then the intermediate paint is sprayed immediately to ensure that molecules between two layers can generate permeation exchange, so as to obtain the nonspecific self-repairing stress immune layer (as shown in figure 3). The intermediate paint is a self-repairing polyurea solution, and the preparation method comprises the following steps:
(2a) preparing GO modified polyurea-based double-wall microcapsules; the graphene oxide modified polyurea-based double-wall microcapsule is prepared by a preparation method disclosed by GO-modified double-walled polyurea microcapsules/epoxy compositions for mineral inorganic self-sealing coating (Materials & Design, Ma Y, Zhang Y, Liu J, et al 2020,189: 108547).
(2b) Preparing polydopamine microspheres; preparing polydopamine by adopting a water phase oxidation method, mixing a 30% ethanol solution and 28% ammonia water according to a volume ratio of 45:1, stirring at 50 ℃, adding 10.5g of a 4.8% dopamine hydrochloride aqueous solution, and stirring for reacting for 8 hours; and centrifuging and washing after the reaction is finished to obtain the polydopamine microsphere.
(2c) Preparing a self-repairing polyurea solution: adding polyether amine into a solvent, uniformly stirring, slowly dripping into isocyanate, controlling the reaction temperature to be 20 ℃, and carrying out prepolymerization for 0.5h after dripping is finished to obtain a prepolymer; adding the polydopamine microspheres and the amino chain extender obtained in the step (2b) into a solvent, uniformly mixing, adding into the prepolymer, controlling the molar ratio of-NCO to NH2 in a reaction system to be 1.05:1, and reacting for 5min to obtain a polydopamine/polyurea elastomer; adding the GO modified polyurea-based double-wall microcapsule obtained in the step (2a) into a polydopamine/polyurea elastomer, and stirring at a high speed to uniformly disperse the GO modified polyurea-based double-wall microcapsule in the polydopamine/polyurea elastomer to obtain a self-repairing polyurea solution.
Wherein said polyetheramine is D2000 and said isocyanate is Hexamethylene Diisocyanate (HDI); the amine chain extender is diethylenetriamine.
The intermediate paint spraying method comprises the following specific steps: adding a certain amount of solvent N, N-dimethylacetamide into the self-repairing polyurea solution obtained in the step (2c) to enable the intermediate paint to reach the spraying standard; then the paint is evenly sprayed on the primer by a spray gun.
(3) Preparation of non-specific lesion self-differentiating immune layer: the thickness of the finish paint film is 150 mu m; the finish paint is two-dimensional material composite polyurethane/polyurea, and the preparation method comprises the following steps: and (2) uniformly mixing the polyether, the solvent I and the emulsifier, dehydrating for 1h at 120 ℃ in vacuum, cooling to 65 ℃, slowly adding an isocyanate monomer, and carrying out prepolymerization for 30min to obtain a prepolymer. Adding the two-dimensional material, the ultraviolet light stabilizer, the heat stabilizer, the polyester polyol and the amino chain extender into the solvent II, uniformly mixing, adding into the prepolymer, and reacting for 0.5h under heat preservation to obtain the two-dimensional material composite polyurethane/polyurea solution. The coating substrate of the finish paint is semi-polyurethane semi-polyurea.
The equivalent ratio of hydroxyl of the polyester polyol-amino chain extender to functional groups of hydroxyl and amino is 0.48:1, the equivalent ratio of NCO to functional groups of hydroxyl and amino in the reaction system is 1.1:1, the using amount of the two-dimensional material is 10 wt% of isocyanate monomer, the using amount of the ultraviolet light stabilizer is 1wt% of isocyanate monomer, and the using amount of the heat stabilizer is 5wt% of isocyanate monomer. The solvent I is N, N-dimethylacetamide, and the solvent II is N, N-dimethylacetamide.
Wherein the polyether is D230; the two-dimensional material is graphene; the isocyanate monomer is Hexamethylene Diisocyanate (HDI); the polyester polyol is ethylene glycol; the amino chain extender is ethylenediamine; the ultraviolet light stabilizer is phenyl salicylate; 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 for spraying the finish paint comprises the following steps: adding a certain amount of solvent N, N-dimethylacetamide into the two-dimensional material composite polyurethane solution to enable the primer to reach the spraying standard; then the paint is evenly sprayed on the primer by a spray gun.
Example 3: in contrast to the embodiment 1, the process of the invention,
in the degraded immune bionic protective coating, the thickness of the formed film of the primer is 150 mu m; the thickness of the intermediate paint film is 400 mu m; the thickness of the formed finish paint film is 250 mu m. The preparation method comprises the following steps:
(1) preparation of specific targeting controlled-release corrosion-inhibition immune layer primer
The same as in example 1.
(2) Preparation of non-specific self-repairing stress immune layer intermediate paint
After the primer in the step (1) is cured, heating to 100 ℃, and immediately spraying intermediate paint toEnsuring separation between two layers The ion can be subjected to osmotic exchangeAnd obtaining the nonspecific self-repairing stress immune layer (as shown in figure 3). The intermediate paint is a self-repairing polyurea solution, and the preparation method comprises the following steps:
(2a) the same as in example 1.
(2b) The same as in example 1.
(2c) Preparing a self-repairing polyurea solution: adding polyether amine into a solvent, uniformly stirring, slowly dripping into isocyanate, controlling the reaction temperature to be 10 ℃, and carrying out prepolymerization for 1h after dripping is finished to obtain a prepolymer; adding the polydopamine microspheres obtained in the step (2b) and an amino chain extender into a solvent, uniformly mixing, adding the mixture into the prepolymer, and controlling-NCO and NH in a reaction system2The molar ratio of the poly (dopamine)/polyurea elastomer is 1.05:1, and the reaction is carried out for 10min to obtain the poly (dopamine)/polyurea elastomer; adding the GO modified polyurea-based double-wall microcapsule obtained in the step (2a) into a polydopamine/polyurea elastomer, and stirring at a high speed to ensure thatThe GO modified polyurea-based double-wall microcapsule is uniformly dispersed in the polydopamine/polyurea elastomer to obtain a self-repairing polyurea solution.
Wherein the polyetheramine is D400, and the isocyanate is dicyclohexylmethane diisocyanate (HMDI), diphenylmethane diisocyanate (MDI); the amino chain extender is 1, 6-hexamethylene diamine.
The intermediate paint spraying method comprises the following specific steps: adding a certain amount of solvent N, N-dimethylacetamide into the self-repairing polyurea solution obtained in the step (2c) to enable the intermediate paint to reach the spraying standard; then the paint is evenly sprayed on the primer by a spray gun.
(3) Preparation of non-specific lesion self-differentiating immune layer: and after the spraying of the primer is finished, keeping the surface temperature not lower than 30 ℃, and immediately spraying the finish to obtain a nonspecific damage self-differentiation immune layer, thereby finishing the preparation of the degraded immune bionic protective coating. The finish paint is a two-dimensional material composite polyurethane/polyurea solution, and the preparation method comprises the following steps: and (2) uniformly mixing the polyether, the solvent I and the emulsifier, dehydrating for 1h at 110 ℃ in vacuum, cooling to 20 ℃, slowly adding an isocyanate monomer, and carrying out prepolymerization for 60min to obtain a prepolymer. Adding the two-dimensional material, the ultraviolet light stabilizer, the heat stabilizer, the polyester polyol and the amino chain extender into the solvent II, uniformly mixing, adding into the prepolymer, and reacting for 3 hours under heat preservation to obtain the two-dimensional material composite polyurethane/polyurea solution. The coating substrate of the finish paint is semi-polyurethane semi-polyurea.
The equivalent ratio of hydroxyl of the polyester polyol-amino chain extender to functional groups of hydroxyl and amino is 0.37:1, the equivalent ratio of NCO to functional groups of hydroxyl and amino in the reaction system is 1.2:1, the using amount of the two-dimensional material is 5wt% of isocyanate monomer, the using amount of the ultraviolet light stabilizer is 0.01 wt% of isocyanate monomer, and the using amount of the heat stabilizer is 1wt% of 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-propylene glycol; the amino chain extender is ethylenediamine; 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 for spraying the finish paint comprises the following steps: adding a certain amount of solvent N, N-dimethylacetamide into the two-dimensional material composite polyurethane/polyurea solution to enable the primer to reach the spraying standard; then the paint is evenly sprayed on the primer by a spray gun.
Example 4: in contrast to the embodiment 1, the process of the invention,
in the degraded immune bionic protective coating, the thickness of the formed film of the primer is 100 mu m; the thickness of the intermediate paint film is 200 μm; the thickness of the finish paint film is 500 mu m. The preparation method comprises the following steps:
(1) preparation of specific targeting controlled-release corrosion-inhibition immune layer primer
Mixing a silane coupling agent KH-570 with an alcohol-water mixture to prepare a diluted solution with the concentration of 1%, adjusting the pH value to 5.5, and standing for hydrolysis for 24 hours. And soaking the preliminarily treated steel structural member I in a silane coupling agent treatment solution for 5min, taking out, and curing at 150 ℃ for 1 hour to obtain a treated steel structural member II. Immediately brushing primer on the surface of the steel structural member II, and then carrying out primary curing for 2h at 55 ℃ to obtain a specific targeted controlled-release corrosion-inhibition immune layer (as shown in figure 2). The primer is prepared by the following method:
carrying out vacuum dehydration on polyoxypropylene glycol at 120 ℃ for 1h, cooling to 60 ℃, and slowly adding a 2, 4-toluene diisocyanate monomer; after the isocyanate monomer is completely added, heating to 80 ℃, adding acetone for multiple times during the heating to reduce the viscosity, and reacting for 1 hour to obtain a prepolymer; uniformly mixing the corrosion inhibitor and the polyhydric alcohol according to a certain proportion, adding the mixture into the prepolymer, cooling to 50 ℃ for reaction for 1h, continuously cooling to room temperature, and adding water for emulsification; finally, vacuum evaporating acetone to obtain the corrosion inhibitor-polyurethane blending system.
(2) Preparation of non-specific self-repairing stress immune layer intermediate paint
After the primer in the step (1) is cured, the temperature is raised to 90 ℃, and then the intermediate paint is sprayed immediately to ensure that molecules between two layers can generate permeation exchange, so as to obtain the nonspecific self-repairing stress immune layer (as shown in figure 3). The intermediate paint is a self-repairing polyurea solution, and the preparation method comprises the following steps:
(2a) preparing GO modified polyurea-based double-wall microcapsules; the graphene oxide modified polyurea-based double-wall microcapsule is prepared by a preparation method disclosed by GO-modified double-walled polyurea microcapsules/epoxy compositions for mineral inorganic self-sealing coating (Materials & Design, Ma Y, Zhang Y, Liu J, et al 2020,189: 108547).
(2b) Preparing polydopamine microspheres; preparing polydopamine by adopting a water phase oxidation method, mixing a 30% ethanol solution and 28% ammonia water according to a volume ratio of 45:1, stirring at 40 ℃, adding 10.5g of a 4.8% dopamine hydrochloride aqueous solution, and stirring for reacting for 10 hours; and centrifuging and washing after the reaction is finished to obtain the polydopamine microsphere.
(2c) Preparing a self-repairing polyurea solution: adding polyether amine into a solvent, uniformly stirring, slowly dripping into isocyanate, controlling the reaction temperature to be 30 ℃, and carrying out prepolymerization for 0.5h after dripping is finished to obtain a prepolymer; adding the polydopamine microspheres and the amino chain extender obtained in the step (2b) into a solvent, uniformly mixing, adding into the prepolymer, controlling the molar ratio of-NCO to NH2 in a reaction system to be 1.2:1, and reacting for 10min to obtain a polydopamine/polyurea elastomer; adding the GO modified polyurea-based double-wall microcapsule obtained in the step (2a) into a polydopamine/polyurea elastomer, and stirring at a high speed to uniformly disperse the GO modified polyurea-based double-wall microcapsule in the polydopamine/polyurea elastomer to obtain a self-repairing polyurea solution.
Wherein said polyetheramine is D2000 and said isocyanate is Hexamethylene Diisocyanate (HDI); the amine chain extender is diethylenetriamine.
The intermediate paint spraying method comprises the following specific steps: adding a certain amount of solvent N, N-dimethylacetamide into the self-repairing polyurea solution obtained in the step (2c) to enable the intermediate paint to reach the spraying standard; then the paint is evenly sprayed on the primer by a spray gun.
(3) Preparation of non-specific lesion self-differentiating immune layer: and after the spraying of the primer is finished, keeping the surface temperature not lower than 30 ℃, and immediately spraying the finish to obtain a nonspecific damage self-differentiation immune layer, thereby finishing the preparation of the degraded immune bionic protective coating. The finish paint is a two-dimensional material composite polyurethane/polyurea solution, and the preparation method comprises the following steps: and (2) uniformly mixing the polyether, the solvent I and the emulsifier, dehydrating for 3h at 100 ℃ in vacuum, cooling to 35 ℃, slowly adding an isocyanate monomer, and carrying out prepolymerization for 15min to obtain a prepolymer. Adding the two-dimensional material, the ultraviolet light stabilizer, the heat stabilizer, the polyester polyol and the amino chain extender into the solvent II, uniformly mixing, adding into the prepolymer, and reacting for 1h under heat preservation to obtain the two-dimensional material composite polyurethane/polyurea solution. The coating substrate of the finish paint is semi-polyurethane semi-polyurea.
The equivalent ratio of hydroxyl of the polyester polyol-amino chain extender to functional groups of hydroxyl and amino is 0.75:1, the equivalent ratio of NCO to functional groups of hydroxyl and amino in the reaction system is 1.1:1, the using amount of the two-dimensional material is 0.5 wt% of isocyanate monomer, the using amount of the ultraviolet light stabilizer is 0.05 wt% of isocyanate monomer, and the using amount of the heat stabilizer is 2 wt% of isocyanate monomer.
Wherein the polyether is polyoxypropylene glycol; the two-dimensional material is montmorillonite; the isocyanate monomer is isophorone diisocyanate (IPDI); the polyester polyol is 1, 6-hexanediol; the amino chain extender is 1, 6-hexamethylene diamine; the ultraviolet light stabilizer is 2, 4-dihydroxy benzophenone; the heat stabilizer is calcium stearate. The solvent I is N, N-dimethylacetamide, and the solvent II is N, N-dimethylacetamide.
The specific method for spraying the finish paint comprises the following steps: adding a certain amount of solvent N, N-dimethylacetamide into the two-dimensional material composite polyurethane/polyurea solution to enable the primer to reach the spraying standard; then the paint is evenly sprayed on the primer by a spray gun.
Example 5: in contrast to the embodiment 1, the process of the invention,
in the degraded immune bionic protective coating, the thickness of the formed film of the primer is 120 mu m; the thickness of the intermediate paint film is 100 mu m; the thickness of the finish paint film is 450 mu m. The preparation method comprises the following steps:
(1) preparation of specific targeting controlled-release corrosion-inhibition immune layer primer
Mixing a silane coupling agent KH-570 with an alcohol-water mixture to prepare a diluted solution with the concentration of 1%, adjusting the pH value to 5.5, and standing for hydrolysis for 36 h. And (3) soaking the preliminarily treated steel structural member I in a silane coupling agent treatment solution for 5min, taking out, and curing at 100 ℃ for 3 hours to obtain a treated steel structural member II. Immediately brushing primer on the surface of the steel structural member II, and then carrying out primary curing for 2h at 55 ℃ to obtain a specific targeted controlled-release corrosion-inhibition immune layer (as shown in figure 2). The primer is prepared by the following method:
carrying out vacuum dehydration on polyoxypropylene glycol at 100 ℃ for 3h, cooling to 50 ℃, and slowly adding a 2, 4-toluene diisocyanate monomer; after the isocyanate monomer is completely added, heating to 70 ℃, adding acetone for multiple times during the heating to reduce the viscosity, and reacting for 2 hours to obtain a prepolymer; uniformly mixing the corrosion inhibitor and the polyhydric alcohol according to a certain proportion, adding the mixture into the prepolymer, cooling to 40 ℃, reacting for 1h, continuously cooling to room temperature, and adding water for emulsification; finally, vacuum evaporating acetone to obtain the corrosion inhibitor-polyurethane blending system.
(2) Preparation of non-specific self-repairing stress immune layer intermediate paint
After the primer in the step (1) is cured, the temperature is raised to 90 ℃, and then the intermediate paint is sprayed immediately to ensure that molecules between two layers can generate permeation exchange, so as to obtain the nonspecific self-repairing stress immune layer (as shown in figure 3). The intermediate paint is a self-repairing polyurea solution, and the preparation method comprises the following steps:
(2a) preparing GO modified polyurea-based double-wall microcapsules; the graphene oxide modified polyurea-based double-wall microcapsule is prepared by a preparation method disclosed by GO-modified double-walled polyurea microcapsules/epoxy compositions for mineral inorganic self-sealing coating (Materials & Design, Ma Y, Zhang Y, Liu J, et al 2020,189: 108547).
(2b) Preparing polydopamine microspheres; preparing polydopamine by adopting a water phase oxidation method, mixing a 30% ethanol solution and 28% ammonia water according to a volume ratio of 45:1, stirring at 50 ℃, adding 10.5g of a 4.8% dopamine hydrochloride aqueous solution, and stirring for reacting for 8 hours; and centrifuging and washing after the reaction is finished to obtain the polydopamine microsphere.
(2c) Preparing a self-repairing polyurea solution: adding polyether amine into a solvent, uniformly stirring, slowly dripping into isocyanate, controlling the reaction temperature to be 2 ℃, and carrying out prepolymerization for 1h after dripping is finished to obtain a prepolymer; adding the polydopamine microspheres and the amino chain extender obtained in the step (2b) into a solvent, uniformly mixing, adding into the prepolymer, controlling the molar ratio of-NCO to NH2 in a reaction system to be 1.1:1, and reacting for 10min to obtain a polydopamine/polyurea elastomer; adding the GO modified polyurea-based double-wall microcapsule obtained in the step (2a) into a polydopamine/polyurea elastomer, and stirring at a high speed to uniformly disperse the GO modified polyurea-based double-wall microcapsule in the polydopamine/polyurea elastomer to obtain a self-repairing polyurea solution.
Wherein said polyetheramine is D2000 and said isocyanate is Hexamethylene Diisocyanate (HDI); the amine chain extender is diethylenetriamine.
The intermediate paint spraying method comprises the following specific steps: adding a certain amount of solvent N, N-dimethylacetamide into the self-repairing polyurea solution obtained in the step (2c) to enable the intermediate paint to reach the spraying standard; then the paint is evenly sprayed on the primer by a spray gun.
(3) Preparation of non-specific lesion self-differentiating immune layer: and after the spraying of the primer is finished, keeping the surface temperature not lower than 30 ℃, and immediately spraying the finish to obtain a nonspecific damage self-differentiation immune layer, thereby finishing the preparation of the degraded immune bionic protective coating. The finish paint is a two-dimensional material composite polyurea solution, and the preparation method comprises the following steps: and (2) uniformly mixing the polyether, the solvent I and the emulsifier, dehydrating for 1h at 110 ℃ in vacuum, cooling to 45 ℃, slowly adding an isocyanate monomer, and carrying out prepolymerization for 5min to obtain a prepolymer. Adding the two-dimensional material, the ultraviolet light stabilizer, the heat stabilizer, the polyester polyol and the amino chain extender into the solvent II, uniformly mixing, adding into the prepolymer, and reacting for 3 hours under heat preservation to obtain the two-dimensional material composite polyurea solution. The coating matrix of the finish paint is pure polyurea.
The equivalent ratio of hydroxyl of the polyester polyol-amino chain extender to functional groups of hydroxyl and amino is 0:1, the equivalent ratio of functional groups of NCO and hydroxyl and amino in the reaction system is 1.2:1, the using amount of the two-dimensional material is 15wt% of isocyanate monomer, the using amount of the ultraviolet light stabilizer is 0.5 wt% of isocyanate monomer, and the using amount of the heat stabilizer is 0.05 wt% of isocyanate monomer.
The polyether is D230; the two-dimensional material is boron nitride; the isocyanate monomer is Toluene Diisocyanate (TDI); the amino chain extender is ethylenediamine; 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 for spraying the finish paint comprises the following steps: adding a certain amount of solvent N, N-dimethylacetamide into the two-dimensional material composite polyurethane/polyurea solution to enable the primer to reach the spraying standard; then the paint is evenly sprayed on the primer by a spray gun.
Example 6: adhesion test and electrochemical test for detecting deteriorated immune bionic protective coating prepared in examples 1-5
Electrochemical test: test pieces required by electrochemical tests are prepared by using a non-coating steel plate, a steel plate coated with a common polyurea coating and the degraded immune bionic protection coating steel plates described in the embodiments 1-5 respectively. The steel plates, 1cm x 1cm in size and 1mm in thickness, were coated with a conventional polyurea coating and the coatings described in examples 1-5, respectively, while uncoated blanks were prepared for comparison. And (3) placing the test piece in 3.5% NaCl solution to be soaked for 3 months, and carrying out potentiodynamic polarization measurement by using a three-electrode system with a steel plate as a working electrode, a saturated calomel electrode as a reference electrode and a titanium net as an auxiliary electrode, wherein the scanning range is +/-250 mV near an open circuit potential, and the scanning speed is 0.5 mV/s. And processing the obtained data by adopting a Tafel extrapolation method to obtain the self-corrosion potential and the corrosion current density.
And (3) adhesion test: the adhesion of the coatings was tested with reference to the regulations in the paint and varnish Pull-open adhesion test (GB/T5210-2006) and adhesion determination test (ASTM-D-4541). The steel plate surface of 10cm x 10cm and 1mm thickness was coated with a conventional polyurea coating (control) and the coatings described in examples 1-5, respectively. Before the test, a smooth and defect-free surface is selected as a test surface, the test surface and the test column are wiped clean by absolute ethyl alcohol, the test column is adhered to the test surface by an acrylic acid adhesive, and the test is carried out after standing for 24 hours.
The test results are shown in table 1.
TABLE 1 test results of electrochemical test and adhesion test
Figure BDA0002864491640000141
As can be seen from the test results of the electrochemical tests in Table 1, the corrosion potential of the uncoated steel sheet after 3 months of immersion was-0.629V, and the corrosion current density was 1.3X 10-5A·cm2(ii) a The steel plate is in an active corrosion state, and the corrosion rate is highest. The corrosion potential of the steel plate coated with the common polyurea coating is positively shifted to-0.487V, and the corrosion current density is reduced to 0.9 multiplied by 10-8A·cm2. The corrosion potential of the samples prepared in examples 1-5 of the present application is-0.366V to-0.196V, and the corrosion current density is 2.9X 10-13～6.0×10-9A·cm2. Therefore, compared with the uncoated steel plate, the corrosion potential of the samples prepared in the examples 1 to 5 of the application is shifted by 0.2 to 0.4V, and the corrosion current density is reduced by 4 to 7 orders of magnitude; the common polyurea coating layer can immunize the corrosion of the steel plate to a certain extent, but compared with the deterioration immune bionic protective coating layer, the deterioration immune bionic protective coating layer can obstruct seawater to a greater extent, so that the corrosion of the steel plate is effectively immunized, the steel plate has a smaller corrosion current density, the corrosion is delayed, and the protection of the steel structure member is better realized.
As can be seen from the results of the adhesion tests in Table 1, the samples prepared in examples 1-5 all had improved bond strengths compared to conventional polyurea coatings. Due to the smaller primer thickness of examples 2 and 4, the silane diffused into the coating to a lesser depth and therefore the bond to the steel sheet surface was weaker than for the other examples; therefore, the damage occurs on the surfaces of the primer and the steel plate, the damage form is similar to that of the common polyurea coating, but the bonding strength is higher than that of the common polyurea coating, which shows that the adhesion between the coating and the surface of the steel structure member can be improved by adopting the coupling agent to treat the surfaces of the primer and the steel plate. The failure interfaces of examples 1,3 and 5 are all inside the coating, indicating that the bond strength of the coating to the steel sheet surface has exceeded the strength of the interior material itself. In addition, in examples 1 to 5, no destruction of the interface between the primer and the intermediate coat or between the intermediate coat and the top coat occurred, indicating that the strength of the interface between the primer and the intermediate coat or between the intermediate coat and the top coat using the interfacial interpenetrating network was not lower than that of the bulk material, and confirming that the three-layer structure had been formed as a bulk interface system.
To sum up, this application for ocean engineering's bionical protective coating of degradation immunity, although by interior to outer in proper order by priming paint, intermediate coat and finish paint three-layer constitution, adjacent two-layer interpenetration in interface department forms the molecule cross-linking interpenetrating network interface, makes three defence lines fuse into an organic whole, has eliminated the key problem that the interface is weak. Moreover, the primer of the protective coating is connected with the surface of the steel structure through a chemical bond, so that the interface bonding force of the coating and the steel structure is improved. In addition, the deteriorated immune bionic protective coating can effectively prevent the corrosion of a steel structure. Therefore, the deteriorated immune bionic protective coating overcomes the problem that the protective coating is easy to damage in the prior art, realizes the protection of a steel structure from two aspects of physical crack repair and chemical corrosion resistance, and has important economic value and social benefit.

Claims (10)

1. The preparation method of the deteriorated immune bionic protective coating for the steel structure engineering is characterized by comprising the following steps of: the method comprises the following steps:
(1) preparing a specific targeting controlled-release corrosion inhibition immune layer: (1a) cleaning the surface of the steel structure, and keeping the surface of the steel structure at certain roughness to obtain a primarily treated steel structure component I; (1b) preparing a silane coupling agent solution, uniformly coating the silane coupling agent solution on the surface of the steel structural member I, and curing for 3-12 hours at room temperature to obtain a treated steel structural member II; (1c) immediately coating a primer on the surface of the steel structural member II to form a film, and then carrying out primary curing for 0.5-2h at 55-60 ℃ to obtain a specific targeted controlled-release corrosion inhibition immune layer; the thickness of the primer film is 80-150 μm, and the primer is a corrosion inhibitor-polyurethane blending system; the corrosion inhibitor is compounded by polyaspartic acid and one or more of polyphosphate, molybdate, organic phosphorus corrosion inhibitor, aluminum powder and zinc powder;
(2) preparing a non-specific self-repairing stress immune layer: after the primer in the step (1) is cured, heating to 80-100 ℃, and immediately spraying intermediate paint to obtain a non-specific self-repairing stress immune layer; the thickness of the intermediate paint film is 100-400 mu m; the intermediate paint is a self-repairing polyurethane-polyurea blending solution, and the preparation method comprises the following steps: (2a) preparing GO modified polyurea-based double-wall microcapsules; (2b) preparing polydopamine microspheres; (2c) preparing a self-repairing polyurea solution: adding polyether amine into a solvent, uniformly stirring, slowly dripping into isocyanate, controlling the reaction temperature to be 2-30 ℃, and carrying out prepolymerization for 0.5-1h after dripping to obtain a prepolymer; adding the polydopamine microspheres and the amine chain extender obtained in the step (2b) into a solvent, uniformly mixing, adding the mixture into the prepolymer, and controlling-NCO and NH in a reaction system2The molar ratio of the poly (dopamine)/polyurea elastomer is 1.05:1-1.2:1, and the reaction lasts for 5-10 min to obtain the poly (dopamine)/polyurea elastomer; adding the GO modified polyurea-based double-wall microcapsule obtained in the step (2a) into a polydopamine/polyurea elastomer, and stirring at a high speed to uniformly disperse the GO modified polyurea-based double-wall microcapsule in the polydopamine/polyurea elastomer to obtain a self-repairing polyurea solution;
(3) preparation of non-specific lesion self-differentiating immune layer: after the intermediate spraying is finished, keeping the surface temperature not lower than 30 ℃, immediately spraying finish paint to obtain a nonspecific damage self-differentiation immune layer, thereby finishing the preparation of the degraded immune bionic protective coating; the film forming thickness of the finish paint is 150-500 mu m; the finish paint is a two-dimensional material composite polyurethane/polyurea solution, and the preparation method comprises the following steps: uniformly mixing polyether, a solvent I and an emulsifier, dehydrating in vacuum at the temperature of 100-120 ℃ for 1-3h, cooling to 20-65 ℃, slowly adding an isocyanate monomer, and carrying out prepolymerization for 5-60min to obtain a prepolymer; adding a two-dimensional material, an ultraviolet light stabilizer, a heat stabilizer, a polyester polyol and an amine chain extender into a solvent II, uniformly mixing, adding into the prepolymer, and carrying out heat preservation reaction for 0.5-3h to obtain a two-dimensional material composite polyurethane/polyurea solution; wherein the equivalent ratio of the hydroxyl group to the functional group of the hydroxyl group and the amino group of the polyester polyol-amine chain extender is (0-0.37):1 or (0.48-1):1, and the equivalent ratio of the functional group of the NCO to the functional group of the hydroxyl group and the amino group in the reaction system is (1.05-1.2): 1; the coating matrix of the finish paint is pure polyurethane, semi-polyurethane semi-polyurea or pure polyurea, and when the coating matrix takes polyurethane as a main body, the polyether used is polyether polyol; when the coating matrix takes polyurea as a main body, the polyether used is polyether amine.
2. The preparation method of the deteriorated immune bionic protective coating for the steel structure engineering according to claim 1, which is characterized in that: in the step (3), the dosage of the two-dimensional material is 0.5-15 wt% of the isocyanate monomer, the dosage of the ultraviolet light stabilizer is 0.01-1wt% of the isocyanate monomer, and the dosage of the heat stabilizer is 0.05-5wt% of the isocyanate monomer.
3. The preparation method of the deteriorated immune bionic protective coating for steel structure engineering according to claim 2, characterized in that: the primer in the step (1c) is prepared by adopting the following method: carrying out vacuum dehydration on polyoxypropylene diol at the temperature of 100-120 ℃ for 1-3h, cooling to 40-60 ℃, and slowly adding an isocyanate monomer; after the isocyanate monomer is completely added, heating to 65-80 ℃, adding acetone for multiple times during the heating to reduce the viscosity, and reacting for 1-2 hours to obtain a prepolymer; uniformly mixing the corrosion inhibitor and the polyhydric alcohol according to a certain proportion, adding the mixture into the prepolymer, cooling to 40-50 ℃, reacting for 1h, continuously cooling to room temperature, and adding water for emulsification; finally, vacuum evaporating acetone to obtain the corrosion inhibitor-polyurethane blending system.
4. The preparation method of the deteriorated immune bionic protective coating for steel structure engineering according to claim 2, characterized in that: the concentration of the silane coupling agent solution in the step (1b) is 0.5-1.0%, and the silane coupling agent is KH-550, KH-560 or KH-570; the silane coupling agent solution is prepared by adopting the following method: mixing a silane coupling agent and an alcohol-water mixture, adjusting the pH value to 3.5-5.5 according to the type of the coupling agent, and standing and hydrolyzing for 24-48 h.
5. The preparation method of the deteriorated immune bionic protective coating for steel structure engineering according to claim 2, characterized in that: the polyether amine in the step (2c) is one or more of D230, D400 and D2000, and the isocyanate is one or more of hexamethylene diisocyanate, dicyclohexyl methane diisocyanate, diphenylmethane diisocyanate, toluene diisocyanate and isophorone diisocyanate; the amine chain extender is one or more of diethyl toluene diamine, dimethyl sulfur toluene diamine, N ' -dialkyl methyl diphenylamine, cyclohexane diamine, chlorinated MDH, ethylene diamine, 1, 3-diaminopropane, 1, 4-diaminobutane, diethylene triamine, pentaethylene hexamine, hexaethylene diamine, tetraethylene pentamine, 1, 6-hexamethylene diamine and 3,3' -4,4' -diamino-diphenylmethane.
6. The preparation method of the deteriorated immune bionic protective coating for steel structure engineering according to claim 2, characterized in that: the specific method for spraying the intermediate paint comprises the following steps: adding a certain amount of solvent N, N-dimethylacetamide into the self-repairing polyurea blending solution obtained in the step (2c) to enable the intermediate paint to reach the spraying standard; then the paint is evenly sprayed on the primer by a spray gun.
7. The preparation method of the deteriorated immune bionic protective coating for steel structure engineering according to claim 2, characterized in that: the preparation method of the polydopamine microsphere in the step (2b) specifically comprises the following steps: preparing polydopamine by adopting a water phase oxidation method, stirring an ethanol solution with a certain concentration and ammonia water at 40-50 ℃, adding a certain amount of dopamine hydrochloride solution, and stirring and reacting for 8-10 hours; and centrifuging and washing after the reaction is finished to obtain the polydopamine microsphere.
8. The preparation method of the deteriorated immune bionic protective coating for steel structure engineering according to claim 2, characterized in that: the polyether amine in the step (3) 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 one or more of hexamethylene diisocyanate, dicyclohexylmethane diisocyanate, diphenylmethane diisocyanate, toluene diisocyanate and isophorone diisocyanate;
the amine chain extender is one or more of diethyl toluene diamine, dimethyl sulfur toluene diamine, N ' -dialkyl methyl diphenylamine, cyclohexane diamine, chlorinated MDH, ethylene diamine, 1, 3-diaminopropane, 1, 4-diaminobutane, diethylene triamine, pentaethylene hexamine, hexaethylene diamine, tetraethylene pentamine, 1, 6-hexamethylene diamine and 3,3' -4,4' -diamino-diphenylmethane;
the ultraviolet light stabilizer is one or more of phenyl salicylate, salicylic acid-4-octylphenyl ester, resorcinol monobenzoate, 2-hydroxy-4-methoxybenzophenone, 2, 4-dihydroxybenzophenone and 2-hydroxy-4-n-octyloxybenzophenone;
the heat stabilizer is one or more of tribasic lead sulfate, dibasic lead phosphite, dibasic lead stearate, cadmium stearate, barium stearate, calcium stearate, lead stearate, zinc stearate, fatty acid salt and maleate.
9. The preparation method of the deteriorated immune bionic protective coating for steel structure engineering according to claim 2, characterized in that: the surface spraying method comprises the following specific steps: adding a certain amount of solvent N, N-dimethylacetamide into the two-dimensional material composite polyurethane/polyurea solution obtained in the step (3) to enable the primer to reach the spraying standard; then the paint is evenly sprayed on the intermediate paint by a spray gun.
10. The deteriorated immune bionic protective coating for steel structure engineering prepared by the method of any one of claims 1 to 9, which is a protective coating on a steel structure substrate, is characterized in that: the deteriorated immune bionic protective coating consists of three layers of primer, intermediate paint and finish paint from inside to outside in sequence; and the two adjacent layers mutually diffuse and are chemically crosslinked to form a molecular crosslinking interpenetrating network; the primer isCorrosion inhibitor-polyurethaneThe corrosion inhibitor is a mixture of polyaspartic acid and one or more of polyphosphate, molybdate, an organic phosphorus corrosion inhibitor, aluminum powder and zinc powder, and the thickness of the formed primer film is 80-150 mu m; the intermediate paint is a self-repairing polyurea blending solution obtained by uniformly dispersing GO modified polyurea-based double-wall microcapsules and polydopamine in a polyurethane-polyurea elastomer, and the thickness of the intermediate paint film is 100-400 mu m; the finish paint is a two-dimensional material composite polyurethane/polyurea solution, and the film forming thickness of the finish paint is 150-700 mu m.
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