CN108822691B - Anticorrosion reinforced self-repairing composite coating - Google Patents
Anticorrosion reinforced self-repairing composite coating Download PDFInfo
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- CN108822691B CN108822691B CN201810749641.5A CN201810749641A CN108822691B CN 108822691 B CN108822691 B CN 108822691B CN 201810749641 A CN201810749641 A CN 201810749641A CN 108822691 B CN108822691 B CN 108822691B
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D163/00—Coating compositions based on epoxy resins; Coating compositions based on derivatives of epoxy resins
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
- C09D175/04—Polyurethanes
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/08—Anti-corrosive paints
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/32—Radiation-absorbing paints
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/014—Additives containing two or more different additives of the same subgroup in C08K
Abstract
The invention discloses an anticorrosion-reinforced self-repairing composite coating, which consists of a base coating and a top coating which are laminated together, wherein the coating of the base coating adopts a component A and a component B, the component A comprises epoxy resin, a self-repairing agent, a corrosion-resistant pigment, a filler, an auxiliary agent and a solvent, and the component B is a curing agent; the paint of the top coating adopts a component A and a component B, wherein the component A comprises high weather-resistant resin, a modified microwave absorbent, a filler, an auxiliary agent and a solvent, and the component B is a curing agent. The invention effectively solves the technical problem that the protective performance of the conventional coating is lost because new protective capacity is formed in time when the coating is damaged.
Description
Technical Field
The invention relates to the technical field of marine corrosion prevention, in particular to a self-repairing composite coating with strengthened corrosion prevention.
Background
The microwave absorbing coating is a compound consisting of polymer and microwave absorbent (hereinafter referred to as absorbent), and the wave absorbing performance of the microwave absorbing coating is closely related to the electromagnetic property of the absorbent, the coating structure and the contact state of the coating substrate. The currently used absorbent is difficult to be prepared into an absolutely precise chemical proportion, contains metal simple substances to different degrees, even if the coating is shielded and protected by polymers, under the influence of multiple factors of high temperature, high humidity and high salt (accelerated polymer aging) in the marine environment, corrosion media (chlorine ion-containing water vapor) can be accelerated to penetrate through the polymer layer to cause iron corrosion, and nonmagnetic substances (such as Fe2O3) are generated to further influence the electromagnetic property of the absorbent; meanwhile, the damage and the cracking of the microwave absorbing coating can be accelerated due to the corrosion of the internal absorbent, the coating can be debonded and even integrally peeled off when the coating is further spread to the bottom layer, and the wave absorbing performance of the coating is irreversibly reduced until the coating fails due to the superposition of all the factors.
Disclosure of Invention
The invention relates to a self-repairing anticorrosive coating and a preparation method thereof, which can effectively solve the technical problem that a new protective capability is formed in time when the coating is damaged and the protective performance of a conventional coating is lost.
In order to achieve the purpose, the invention adopts the technical scheme that: a self-repairing composite coating with reinforced anticorrosion is composed of a base coating and a surface coating which are laminated together, and is characterized in that:
the coating of the base coat adopts a component A and a component B, wherein the component A comprises epoxy resin, a self-repairing agent, a corrosion-resistant pigment, a filler, an auxiliary agent and a solvent, and the component B is a curing agent; the self-repairing agent is a nano microsphere material with a core-shell structure, the corrosion-resistant pigment is a mixture of more than two of zinc phosphate, zinc chromate, zinc molybdate or mica iron oxide, the auxiliary agent is BYK142 and/or BYK320, the filler is one or a mixture of more of titanium dioxide, silicon dioxide, mica powder and barite, the solvent is formed by mixing butyl acetate and xylene, and the component B curing agent is polyamide 650;
the paint of the surface coating adopts a component A and a component B, wherein the component A comprises high weather-resistant resin, a modified microwave absorbent, a filler, an auxiliary agent and a solvent, and the component B is a curing agent; the modified microwave absorbent is a nano microsphere material containing the microwave absorbent, the filler is one or a mixture of more of titanium dioxide, silicon dioxide, mica powder and calcium carbonate, the auxiliary agent is one or a mixture of more of organic bentonite slurry, BYK2155 and BYK405, the solvent is formed by mixing butanol/n-butanol, butyl acetate and xylene, and the component B curing agent is an HDI curing agent.
The technical scheme can further comprise that: the coating of the base coat comprises the following components in parts by weight: 35-65 parts of epoxy resin, 5-15 parts of corrosion-resistant pigment, 5-20 parts of self-repairing agent, 10-40 parts of filler, 0.1-3 parts of wetting dispersant, 0.1-3 parts of flatting agent, 10-30 parts of solvent and 40-50 parts of curing agent, wherein the A component and the B component are mixed according to the weight percentage ratio of epoxy equivalent to amine hydrogen equivalent of 1: 1 for use.
The technical scheme can further comprise that: the top coating paint comprises the following components in parts by weight: 30-60 parts of resin, 30-60 parts of modified microwave absorbent, 1-20 parts of filler, 0.5-3 parts of wetting dispersant, 0.5-3 parts of flatting agent, 10-30 parts of solvent and 15-30 parts of curing agent, wherein the A component and the B component are mixed according to the weight percentage ratio of epoxy equivalent to amine hydrogen equivalent of 1: 1.
The technical scheme can further comprise that: the solvent of the bottom coating is formed by mixing 10-30 parts of butyl acetate and 30-70 parts of dimethylbenzene.
The technical scheme can further comprise that: the solvent of the surface coating is formed by mixing 10-25 parts of n-butyl alcohol/butanol, 10-30 parts of butyl acetate and 30-50 parts of dimethylbenzene.
The technical scheme can further comprise that: the self-repairing agent is a micron-sized composite microsphere material with a core-shell structure, wherein the shell is a porous silicon dioxide inorganic substance, and the core is one or more sustained-release agents.
The technical scheme can further comprise that: the modified microwave absorbent is a micron-sized composite microsphere material with a core-shell structure, wherein the shell is a porous silicon dioxide inorganic substance, and the core is a microwave absorbent which is a mixture or alloy of carbonyl iron and one or more of nickel carbonyl and cobalt.
The technical scheme can further comprise that: the high weather-resistant resin is acrylic resin or polysiloxane resin.
The technical scheme can further comprise that: the HDI curing agent comprises one or more of N-75, 3900, PU740, PU540 and the like.
The technical scheme of the method for preparing the self-repairing functional additive is as follows: adding hexadecyl trichlorosilane dropwise into absolute ethyl alcohol, ultrasonically stirring, slowly adding tetraethoxysilane at the peripheral linear velocity of a stirring blade of 1-2 m/s, ultrasonically stirring, then sequentially adding ammonia water and water at the peripheral linear velocity of the stirring blade of 1 m/s, reacting for 7 hours, filtering, washing with water and washing with alcohol, drying at 40 ℃ in vacuum for 5 hours to obtain mesoporous silica hollow microspheres, dispersing the microspheres into an aqueous solution containing a corrosion inhibitor, stirring, dispersing for 2 hours at the peripheral linear velocity of the stirring blade of 3-5 m/s, standing for 12 hours, filtering, and drying to obtain the self-repairing functional additive.
In conclusion, the beneficial effects of the invention are as follows:
according to the microwave absorption coating, the self-repairing material is introduced into the bottom coating, so that when the coating is damaged and the metal substrate is exposed, a protective film is formed on the surface of the exposed metal substrate by virtue of the corrosion inhibitor released by the self-repairing material microspheres, further corrosion is prevented, and the corrosion protection capability of the coating on the metal is improved; the modified microwave absorbent prepared by loading the self-repairing material on the surface of the particle of the conventional microwave absorbent can provide a protection mechanism for the absorbent when corrosive media invade, so that the corrosion resistance of the absorbent is improved, and the microwave absorption coating (surface layer) prepared by the modified microwave absorbent fundamentally overcomes the problems of corrosion and deterioration of the conventional microwave absorption coating due to easy corrosion of the absorbent; and the self-repairing anticorrosion strengthening function of the microwave absorbing coating is realized by laminating and compounding the bottom layer and the surface layer, and the coating is particularly suitable for long-term use of the microwave absorbing coating in heavy corrosion environments such as marine climate and the like.
When the components are in specific weight proportion, the component A and the component B introduced in the summary of the invention are mixed according to the weight percent, especially when the component A and the component B are mixed according to the weight percent ratio of epoxy equivalent to amine hydrogen equivalent of 1: 1, the comprehensive performances of the coating such as hardness, adhesive force, flexibility, corrosion resistance, microwave reflection performance and the like reach the optimal state.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is further described in detail below with reference to examples, and the exemplary embodiments and descriptions thereof are only used for explaining the present invention and are not used as limitations of the present invention.
Example 1
The coating adopts a bottom-surface double-layer structure design, and the formula design of each layer of coating adopts a two-component system and is weighed according to the weight percentage.
Ratio of priming paint
The component A resin is bisphenol A epoxy resin with an epoxy equivalent of between 210 and 450, and can be Hensmei 6101, Dow 671 or a mixture thereof.
The anti-corrosion filler in the component A is compound zinc phosphate, the grain diameter is less than 3 microns, and can be ZNP of Basff, ZP-10 of Kbabai and the like.
The self-repairing agent in the component A is an inorganic capsule structural material filled with corrosion inhibition liquid, and the preparation method comprises the following steps: 200ml of absolute ethyl alcohol is dripped with 0.015g of hexadecyl trichlorosilane, ultrasonic/stirring is carried out, 5ml of ethyl orthosilicate is slowly added, 6ml of ammonia water and 50ml of water are sequentially added after ultrasonic/stirring (the peripheral linear velocity of a stirring blade is 1-2 m/s), after 7 hours of reaction, filtration, water washing and alcohol washing are carried out, after 5 hours of vacuum drying at 40 ℃, mesoporous silica hollow microspheres are obtained, the microspheres are dispersed into 0.5g/L benzotriazole solution, after 2 hours of stirring and dispersion (the peripheral linear velocity of the stirring blade is 1-2 m/s), after 12 hours of standing, filtration is carried out, and after 30 ℃ and 6 hours of drying, the self-repairing agent A material is obtained.
The solvent for the component A is prepared by mixing 5-10 parts of n-butyl alcohol and 10-20 parts of dimethylbenzene.
The component B curing agent is a polyamide epoxy curing agent which can be 650 and V115.
The component A and the component B are mixed according to the weight percentage ratio of epoxy equivalent to amine hydrogen equivalent of 1: 1 for use.
Top coat paint ratio
The component A resin is hydroxy acrylic resin, and can be Acoma 854, 878.
The modified microwave absorbent in the component A is a micron-sized composite microsphere material with a core-shell structure and containing the microwave absorbent, and the preparation method comprises the following steps: firstly, placing 12 parts of carbonyl iron powder (with the particle size of 1 micron) and 3 parts of carbonyl cobalt powder (with the particle size of 1 micron) in an absolute ethyl alcohol solution, uniformly stirring, placing in a ball mill, ball-milling and dispersing for 5 hours, drying at 50 ℃ in vacuum for 3 hours to obtain powder A, and then physically stirring and blending 10 parts of powder A and 2 parts of self-repairing agent dry powder for 2 hours to obtain the modified microwave absorbent.
The solvent used in the component A is prepared by mixing 5-10 parts of cyclohexanone, 5-10 parts of butyl acetate and 15-30 parts of dimethylbenzene.
The component B curing agent is HDI curing agent, and may be one of N-75, 3390 and other curing agents.
The component A and the component B are mixed according to the weight percentage ratio of epoxy equivalent to amine hydrogen equivalent of 1: 1 for use.
Example 2
The preparation method and the process are the same as those of the example 1, and only the proportion of the coating components is changed.
Primer formula of composite microwave absorbing coating-two-component epoxy polyamide system
The component A and the component B are mixed according to the weight percentage ratio of epoxy equivalent to amine hydrogen equivalent of 1: 1 for use.
Double-component acrylic polyurethane system as composite microwave absorbing coating surface paint formula
The component A and the component B are mixed according to the weight percentage ratio of epoxy equivalent to amine hydrogen equivalent of 1: 1 for use.
Example 3
The preparation method and the process are the same as those of the example 1, and only the proportion of the coating components is changed.
Primer formula of composite microwave absorbing coating-two-component epoxy polyamide system
The component A and the component B are mixed according to the weight percentage ratio of epoxy equivalent to amine hydrogen equivalent of 1: 1 for use.
Double-component acrylic polyurethane system as composite microwave absorbing coating surface paint formula
The component A and the component B are mixed according to the weight percentage ratio of epoxy equivalent to amine hydrogen equivalent of 1: 1 for use.
Example 4
The preparation method and the process are the same as those of the example 1, and only the proportion of the coating components is changed.
Primer formula of composite microwave absorbing coating-two-component epoxy polyamide system
The component A and the component B are mixed according to the weight percentage ratio of epoxy equivalent to amine hydrogen equivalent of 1: 1 for use.
Double-component acrylic polyurethane system as composite microwave absorbing coating surface paint formula
The component A and the component B are mixed according to the weight percentage ratio of-NCO to-OH which is 1: 1 for use.
Comparative example 1
Compared with the formulation of the example 1, the self-repairing agent is not contained in the formulation of the primer, and other components are the same.
Comparative example 2
Compared with the example 1, the formulation of the primer does not contain the zinc phosphate corrosion resistant pigment which can act synergistically with the self-repairing agent, and the iron oxide red corrosion resistant pigment is replaced by the zinc phosphate corrosion resistant pigment, and other components are the same.
Comparative example 3
Compared with the example 1, the formula of the primer coating does not contain a self-repairing agent, carbonyl iron powder and carbonyl cobalt powder (conventional microwave absorbing materials) are used for replacing a modified microwave absorbent in the formula of the surface coating, and other components are the same.
Coating panels prepared according to the standard spray coating method of examples 1-4 and comparative examples 1-3 were subjected to the performance test, and the results are shown in Table 1
Table 1 comparison of various properties
From the test results, compared with comparative examples 1, 2 and 3 which do not contain self-repairing agent components or zinc phosphate corrosion resistant pigments, the salt spray resistance (scratch test) of examples 1 to 4 of the invention has obvious advantages on the premise of keeping the microwave reflection performance equivalent, compared with comparative example 3 which adopts the conventional microwave absorbent, on the premise of keeping the microwave reflection performance equivalent, the salt water resistance, the salt spray resistance (no scratch) and the salt spray resistance (scratch) of examples 1 to 4 which adopt the self-repairing agent and the modified microwave absorbent have obvious advantages, and the microwave reflection rate test results before and after the salt spray test (scratch) show that the microwave reflection performance of the coating is obviously reduced after the occurrence of rust (the minimum value of the microwave reflection rate of comparative examples 1 and 2 is increased by 12 percent, and the minimum value of the microwave reflection rate of comparative example 3 is increased by 38 percent), the composite coating has better corrosion resistance and can maintain the microwave absorption performance in a corrosive environment for a long time.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents, improvements and the like that fall within the spirit and principle of the present invention are intended to be included therein.
The above description is only for the preferred embodiment of the present invention and not for the limitation of the protection scope of the present invention, it should be noted that, for those skilled in the art, modifications or equivalent substitutions can be made on the technical solution of the present invention without departing from the principle of the present invention, and these modifications or equivalent substitutions should also be regarded as the protection scope of the present invention.
Claims (8)
1. A self-repairing composite coating with reinforced anticorrosion is composed of a base coating and a surface coating which are laminated together, and is characterized in that: the coating of the base coat adopts a component A and a component B, wherein the component A comprises epoxy resin, a self-repairing agent, a corrosion-resistant pigment, a filler, an auxiliary agent and a solvent, and the component B is a curing agent; the self-repairing agent is a micron-sized composite microsphere material, the corrosion-resistant pigment is a mixture of more than two of zinc phosphate, zinc chromate, zinc molybdate or mica iron oxide, the auxiliary agent is BYK142 and/or BYK320, the filler is one or a mixture of more of titanium dioxide, silicon dioxide, mica powder and barite, the solvent is formed by mixing butyl acetate and xylene, and the component B curing agent is polyamide 650;
the coating of the base coat comprises the following components in parts by weight: 35-65 parts of epoxy resin, 5-20 parts of self-repairing agent, 1-15 parts of corrosion-resistant pigment, 10-40 parts of filler, 0.1-3 parts of wetting dispersant, 0.1-3 parts of flatting agent, 10-30 parts of solvent and 40-50 parts of curing agent, wherein the A component and the B component are mixed according to the weight percentage ratio of epoxy equivalent to amine hydrogen equivalent of 1: 1;
the paint of the surface coating adopts a component A and a component B, wherein the component A comprises high weather-resistant resin, a modified microwave absorbent, a filler, an auxiliary agent and a solvent, and the component B is a curing agent; the modified microwave absorbent is a micron-sized composite microsphere material with a core-shell structure and containing the microwave absorbent, the filler is one or a mixture of more of titanium dioxide, silicon dioxide, mica powder and calcium carbonate, the auxiliary agent is one or a mixture of more of organic bentonite slurry, BYK2155 and BYK405, the solvent is formed by mixing butanol/n-butanol, butyl acetate and xylene, and the component B curing agent is an HDI curing agent;
the top coating paint comprises the following components in parts by weight: 30-60 parts of resin, 30-60 parts of modified microwave absorbent, 1-20 parts of filler, 0.5-3 parts of wetting dispersant, 0.5-3 parts of flatting agent, 15-30 parts of solvent and 15-30 parts of curing agent, wherein the A component and the B component are mixed according to the weight percentage ratio of epoxy equivalent to amine hydrogen equivalent of 1: 1.
2. The corrosion-protected enhanced self-healing composite coating of claim 1, wherein: the solvent of the bottom coating is formed by mixing 10-30 parts of butyl acetate and 30-70 parts of dimethylbenzene.
3. The corrosion-protected enhanced self-healing composite coating of claim 1, wherein: the solvent of the surface coating is formed by mixing 10-25 parts of n-butyl alcohol/butanol, 10-30 parts of butyl acetate and 30-50 parts of dimethylbenzene.
4. The corrosion-protected enhanced self-healing composite coating of claim 1, wherein: the self-repairing agent is a micron-sized composite microsphere material, wherein the shell is a porous silicon dioxide inorganic substance, and the core is one or more sustained-release agents.
5. The corrosion-protected enhanced self-healing composite coating of claim 1, wherein: the modified microwave absorbent is a micron-sized composite microsphere material with a core-shell structure, wherein the shell is a porous silicon dioxide inorganic substance, and the core is a microwave absorbent which is a mixture or alloy of carbonyl iron and one or more of nickel carbonyl and cobalt.
6. The corrosion-protected enhanced self-healing composite coating of claim 1, wherein: the high weather-resistant resin is acrylic resin or polysiloxane resin.
7. The corrosion-protected enhanced self-healing composite coating of claim 1, wherein: the HDI curing agent comprises one or more of N-75, 3900, PU740, PU540 and the like.
8. The corrosion-protected enhanced self-healing composite coating of claim 1, wherein: the curing agent is one or more polyamide 650 epoxy curing agents.
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| CN110452600B (en) * | 2019-07-30 | 2021-09-14 | 博罗县东明化工有限公司 | Self-repairing heavy-duty anticorrosive coating and preparation method thereof |
| CN110698962A (en) * | 2019-10-22 | 2020-01-17 | 西北工业大学 | Composite material with self-repairing performance and anti-corrosion performance and preparation method thereof |
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| CN111205745B (en) * | 2020-01-09 | 2021-04-20 | 厦门双瑞船舶涂料有限公司 | Self-repairing anticorrosive coating and preparation method thereof |
| CN111423789B (en) * | 2020-05-28 | 2022-03-25 | 北京环境特性研究所 | Self-repairing electromagnetic functional coating and preparation method thereof |
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| JP2017218519A (en) * | 2016-06-08 | 2017-12-14 | 国立大学法人 鹿児島大学 | Self-recovery material and method for producing repairing agent-containing microcapsule |
| CN106398473A (en) * | 2016-09-12 | 2017-02-15 | 国网山东省电力公司电力科学研究院 | Rusted zinc repair coating |
| CN106634424A (en) * | 2016-12-15 | 2017-05-10 | 福建百花化学股份有限公司 | Water-based epoxy anti-corrosion primer |
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| CN107446464A (en) * | 2017-07-20 | 2017-12-08 | 中国科学院过程工程研究所 | Polymeric coating material and preparation method with Corrosion monitoring and self-repair function |
| CN107760163A (en) * | 2017-11-05 | 2018-03-06 | 青岛农业大学 | A kind of selfreparing corrosion-inhibiting coating with anti-pollution function and preparation method thereof |
| CN108102456A (en) * | 2017-12-18 | 2018-06-01 | 天津大学 | A kind of double microcapsule compositions of self-repair function and the application on self-repair function protective coating |
| CN108003688A (en) * | 2017-12-25 | 2018-05-08 | 王文婧 | A kind of preparation method of selfreparing anti-corrosion primer |
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