CN108485495A - A method of preparing the self-test anticorrosive paint containing nano-carrier - Google Patents

A method of preparing the self-test anticorrosive paint containing nano-carrier Download PDF

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CN108485495A
CN108485495A CN201810256020.3A CN201810256020A CN108485495A CN 108485495 A CN108485495 A CN 108485495A CN 201810256020 A CN201810256020 A CN 201810256020A CN 108485495 A CN108485495 A CN 108485495A
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carrier
nano
mixed liquor
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test
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CN108485495B (en
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李静
崔锦灿
姜志远
冯庆康
袁茜
杨俊和
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University of Shanghai for Science and Technology
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    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09DCOATING 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
    • C09D175/00Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
    • C09D175/04Polyurethanes
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    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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    • C08K5/00Use of organic ingredients
    • C08K5/16Nitrogen-containing compounds
    • C08K5/34Heterocyclic compounds having nitrogen in the ring
    • C08K5/3412Heterocyclic compounds having nitrogen in the ring having one nitrogen atom in the ring
    • C08K5/3432Six-membered rings
    • C08K5/3437Six-membered rings condensed with carbocyclic rings
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    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K9/00Use of pretreated ingredients
    • C08K9/12Adsorbed ingredients, e.g. ingredients on carriers
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    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09DCOATING 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
    • C09D133/00Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
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    • C09DCOATING 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
    • C09D163/00Coating compositions based on epoxy resins; Coating compositions based on derivatives of epoxy resins
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09DCOATING 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
    • C09D5/00Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/08Anti-corrosive paints
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    • C09D7/00Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40Additives
    • C09D7/60Additives non-macromolecular
    • C09D7/61Additives non-macromolecular inorganic
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    • C09D7/00Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40Additives
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    • C09D7/00Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40Additives
    • C09D7/70Additives characterised by shape, e.g. fibres, flakes or microspheres
    • GPHYSICS
    • G01MEASURING; TESTING
    • G01NINVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N21/00Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
    • G01N21/75Systems in which material is subjected to a chemical reaction, the progress or the result of the reaction being investigated
    • G01N21/77Systems in which material is subjected to a chemical reaction, the progress or the result of the reaction being investigated by observing the effect on a chemical indicator
    • G01N21/78Systems in which material is subjected to a chemical reaction, the progress or the result of the reaction being investigated by observing the effect on a chemical indicator producing a change of colour
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    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
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Abstract

The method for preparing the self-test anticorrosive paint containing nano-carrier includes the following steps:Step 1 prepares nano-carrier and configures the nano-carrier aqueous solution of proportional concentration;Nano-carrier aqueous solution and self-test substance that show color are mixed to get the first mixed liquor by step 2 in proportion;Step 3 obtains the second mixed liquor after the first mixed liquor is carried out ultrasonic disperse;Step 4 filters in the second mixed liquor of removal and obtains solid matter after unreacted solution, proportional third mixed liquor will be matched after solid matter plus water;Step 5, third mixed liquor is mixed with film forming matrix, nano-carrier is graphene, nm-class boron nitride, nanoclay and layered double-hydroxide lamella, self-test substance that show color is thymol blue, fluorescein, oxyquinoline, 1,10 Phens, 1,10 Phen pentaaminos and phenolphthalein, film forming matrix are aqueous organic resin, and aqueous organic resin is aqueous polyurethane, water-based acrylic resin and aqueous epoxy resins.

Description

A method of preparing the self-test anticorrosive paint containing nano-carrier
Technical field
The present invention relates to a kind of preparation methods of anticorrosive paint, belong to chemical field.
Background technology
Organic coating is current Metal surface anti-corrosion method most common in production.But when by using for a long time Afterwards, the organic coating on metal surface generates stripping so as to cause substrate since corrosion occurs for protecting group bottom with interlayer is applied, in turn Lead to the failure of organic coating defencive function.It is rotten when generating macroscopic corrosion product in the corrosion process of metal surface Degree of corrosion is extremely serious, so if there is a kind of painting that can be carried out self and detect and can be warned in the early period of corrosion It is applied to the anti-corrosion effect that Metal surface anti-corrosion will greatly improve metal by material.
Invention content
The present invention is to carry out to solve the above-mentioned problems, and it is an object of the present invention to provide a kind of preparing the self-test containing nano-carrier The method for surveying anticorrosive paint.
The present invention provides a kind of methods preparing the self-test anticorrosive paint containing nano-carrier, have the feature that, Include the following steps:Step 1 prepares nano-carrier and configures the nano-carrier aqueous solution of proportional concentration;Step 2, Nano-carrier aqueous solution and self-test substance that show color are mixed to get the first mixed liquor in proportion;Step 3, by the first mixed liquor The second mixed liquor is obtained after carrying out ultrasonic disperse;Step 4 filters in the second mixed liquor of removal and obtains solid-state after unreacted solution Substance will match proportional third mixed liquor after solid matter plus water;Step 5, by third mixed liquor and film forming matrix It is mixed to get anticorrosive paint, wherein nano-carrier is graphene, nm-class boron nitride, nanoclay and layered double-hydroxide piece In layer any one or mixtures thereof, the mass percent of nano-carrier is 0.4%~4%, and self-test substance that show color is hundred In phenol indigo plant, fluorescein, oxyquinoline, 1,10 Phens (1,10-Phenanthroline), 1,10 Phen pentaaminos In (1,10-phenanthroline-5-amine) and phenolphthalein any one or mixtures thereof, film forming matrix is aqueous to have Machine resin, aqueous organic resin are any one or its in aqueous polyurethane, water-based acrylic resin and aqueous epoxy resins Mixture, mass percent >=94% of aqueous organic resin.
In the method provided by the invention for preparing the self-test anticorrosive paint containing nano-carrier, can also have such Feature:Wherein, the mass percent of self-test substance that show color is 0.2%~2%.
In the method provided by the invention for preparing the self-test anticorrosive paint containing nano-carrier, can also have such Feature:Wherein, in step 1, prepare nano-carrier and be configured to normal concentration be 1mg/ml~5mg/ml nano-carrier it is water-soluble Liquid;In step 2, by nano-carrier solution and self-test substance that show color in mass ratio 0.9~3.5:0.3~1.8 ratio mixing Obtain the first mixed liquor;In step 4, the third mixed liquor for being 1mg/ml~5mg/ml by proportioning after solid matter plus water.
The effect of invention
According to the method according to the present invention for preparing the self-test anticorrosive paint containing nano-carrier, nanometer is taken to load skill Art is used for preparing a kind of smart coatings, as the carrier of self-test substance that show color, has the work(for loading and discharging color developing agent in due course Can, so the method preparation according to the present invention for preparing the self-test anticorrosive paint containing nano-carrier allows color developing agent uniformly to mix Close in coating so that macroscopic color change occurs at the initial stage that steel plate corrosion reaction occurs, play automatic detection and The effect of early warning makes coating that there is excellent Corrosion Protection, this method to prepare coating in addition, this method is used to prepare coating All belong to environmental protection coating material without using volatile organic matter in whole preparation process.
Description of the drawings
Fig. 1 is the photograph of the self-test coloring function of coating when iron plate surface is just corroded in the embodiment of the present invention one Piece;
Fig. 2 is the photo of the self-test coloring function of coating in the embodiment of the present invention one after etching time extension;
Fig. 3 is that Fe is not added in the embodiment of the present invention one, two, three2+The photo of painting color before ion;And
Fig. 4 is that Fe is added in the embodiment of the present invention one, two, three2+The photo of painting color after ion.
Specific implementation mode
It is real below in order to make the technical means, the creative features, the aims and the efficiencies achieved by the present invention be easy to understand Example combination attached drawing is applied to be specifically addressed a kind of method preparing the self-test anticorrosive paint containing nano-carrier of the present invention.
<Embodiment one>
The self-test preparation method of anticorrosion paint containing nano-carrier of the present embodiment and application include the following steps:
Step 1 carries out preparing graphene oxide, and is configured to a concentration of 2mg/ml's with improvement Hummer ' s methods Graphene oxide water solution.
Step 2, by graphene oxide water solution and 1,10 Phens in mass ratio 2:1 ratio is mixed to get first Mixed liquor.
First mixed liquor is carried out ultrasonic disperse in the Ultrasound Instrument that ultrasonic power is 300W and obtained after ten minutes by step 3 Second mixed liquor.
Step 4 filters in the second mixed liquor of removal and obtains solid matter after unreacted solution, after solid matter plus water Match into the third mixed liquor of 2mg/ml.
Third mixed liquor and waterborne polyurethane resin are mixed to get anticorrosive paint, wherein coating total solid matters by step 5 Resin quality percentage is 99.4% in matter, graphene oxide mass percent 0.4%, 1,10 Phen mass percent 0.2%.
Step 6, the mass percent of coating total solid substance is adjusted to by addition deionized water in above-mentioned anticorrosive paint 20%.
Coating after addition deionized water in step 6 is coated in stick coating method after iron plate surface forms film and is put by step 7 Baking oven carries out drying and processing at a temperature of 110 DEG C, is taken out after 30 minutes, obtains the coating formed on iron plate surface.
<Embodiment two>
The self-test preparation method of anticorrosion paint containing nano-carrier of the present embodiment and application include the following steps:
Step 1 carries out preparing graphene oxide, and is configured to a concentration of 2mg/ml's with improvement Hummer ' s methods Graphene oxide water solution.
Step 2, by graphene oxide water solution and 1,10 Phen pentaaminos in mass ratio 2:1 ratio mixes To the first mixed liquor.
First mixed liquor is carried out ultrasonic disperse in the Ultrasound Instrument that ultrasonic power is 300W and obtained after ten minutes by step 3 Second mixed liquor.
Step 4 filters in the second mixed liquor of removal and obtains solid matter after unreacted solution, after solid matter plus water Match into the third mixed liquor of 2mg/ml.
Third mixed liquor and waterborne polyurethane resin are mixed to get anticorrosive paint, wherein coating total solid matters by step 5 Resin quality percentage is 94% in matter, graphene oxide mass percent 4%, 1,10 Phen pentaamino mass percent 2%.
Step 6, the mass percent of coating total solid substance is adjusted to by addition deionized water in above-mentioned anticorrosive paint 20%.
Step 7 puts the coating stick coating method after addition deionized water in step 6 after being coated in iron plate surface and forming film Enter baking oven, drying and processing is carried out at a temperature of 110 DEG C, is taken out after 30 minutes, obtains the coating formed on iron plate surface.
<Embodiment three>
The self-test preparation method of anticorrosion paint containing nano-carrier of the present embodiment and application include the following steps:
Step 1 carries out preparing graphene oxide, and is configured to a concentration of 2mg/ml's with improvement Hummer ' s methods Graphene oxide water solution adds 0.3 times of the hydrazine hydrate no more than graphene quality, obtains to graphene oxide carry out portion Divide the graphene aqueous solution after reduction.
Step 2, by the graphene aqueous solution and 1,10 Phens in mass ratio 2 after above-mentioned partial reduction:1 ratio It is mixed to get the first mixed liquor.
First mixed liquor is carried out ultrasonic disperse in the Ultrasound Instrument that ultrasonic power is 300W and obtained after ten minutes by step 3 Second mixed liquor.
Step 4 filters in the second mixed liquor of removal and obtains solid matter after unreacted solution, after solid matter plus water Match into the third mixed liquor of 2mg/ml.
Third mixed liquor and waterborne polyurethane resin are mixed to get anticorrosive paint, wherein coating total solid matters by step 5 Resin quality percentage is 97% in matter, graphene oxide mass percent 2%, 1,10 Phen mass percent 1%.
Step 6, the mass percent of coating total solid substance is adjusted to by addition deionized water in above-mentioned anticorrosive paint 20%.
Step 7 puts the coating stick coating method after addition deionized water in step 6 after being coated in iron plate surface and forming film Enter baking oven, drying and processing is carried out at a temperature of 110 DEG C, is taken out after 30 minutes, obtains the coating formed on iron plate surface.
The graphene of different reducing degrees prepared by above-described embodiment one to embodiment three and different self-tests The chemical property very rotundity for the composite material aqueous solution that substance that show color is formed, after which places 48 hours Apparent lamination is not observed to occur.Meanwhile load made above have self-test develop the color the graphene to be formed with The mixed coatings chemistry performance of aqueous polyurethane is also sufficiently stable, after the coating placement 48 hours, is also not observed apparent Lamination occur.
Fig. 1 is the photograph of the self-test coloring function of coating when iron plate surface is just corroded in the embodiment of the present invention one Piece.
As shown in Figure 1, it can be seen that iron plate is after room temperature rod coating, and the coating of iron plate maintains the good transparency, in iron Plate generation corrosion initial stage produces macroscopic color change, and the chromogenic reaction of coating is sensitive.
Fig. 2 is the photo of the self-test coloring function of coating in the embodiment of the present invention one after etching time extension.
As shown in Fig. 2, the iron plate in figure is to be immersed in containing 3.5% NaCl aqueous solutions after rod coating coating in embodiment one Iron plate after 1 day, it can be seen that apparent metachromatism occurs in the coating of iron plate, illustrates that large area corruption has occurred in base metal Erosion, the coating for also demonstrating the preparation of embodiment one have self-test coloring function.
Fig. 3 is that Fe is not added in the embodiment of the present invention one, two, three2+The photo of painting color before ion.
As shown in figure 3, drawing is from left to right followed successively by embodiment one, embodiment two and embodiment three Fe is not added in Fig. 32+ The coating containing self-test substance that show color before ion, it can be seen that coating is sufficiently stable, also indicates that and adds containing nanometer load The smart coatings of the self-test substance that show color of body load do not change paint stability.
Fig. 4 is that Fe is added in the embodiment of the present invention one, two, three2+The photo of painting color after ion.
As shown in figure 4, drawing is from left to right followed successively by embodiment one, embodiment two and the addition of embodiment three Fe in Fig. 42+From The coating containing self-test substance that show color after son, produces apparent color change.This shows to be prepared by nanometer loading technology The smart coatings containing self-test substance that show color efficiently solve loading, dispersion and release etc. of the color developing agent in coating and ask Topic, and the feature of color developing agent itself is remained simultaneously, it can be used for preparing the self-test coloring function with good corrosion resistance Coating and its coating.
The effect of embodiment
In a preferred embodiment of the invention, nano-carrier selects graphene in preparation method.Graphene can be selected from oxygen Graphite alkene, the graphene oxide of partial reduction and the graphene through surface chemical modification.In a more preferred embodiment, graphite Alkene uses graphene oxide, such as the graphene oxide solution form prepared by improveing Hummer ' s methods may be used.Pass through Partial reduction or surface chemical modification graphene regulate and control the functional group of graphene surface, to control nano-carrier for self-test Survey the loading functional of colour developing molecule.In a preferred embodiment of the invention, the graphene oxide of partial reduction can be by using It is prepared by reducing agent.Reducing agent can be selected from hydrazine and its derivative, vitamin C and glucose.It is used in graphene by improveing In the case of graphene oxide solution form prepared by Hummer ' s methods, reducing agent preferably uses micro (less than graphite oxide The quality of alkene) hydrazine hydrate.Graphene and its derivative have both good physical barrier property and extra specific surface area.One side Face can be used as the barrier in coating, enhance the corrosion resistance of coating;On the other hand, the carrier as self-test colour developing molecule, rises To the function of loading and discharge color developing agent in due course.
In addition, in a preferred embodiment of the invention, it is adjacent luxuriant and rich with fragrance can be selected from 1,10 for self-test colour developing molecule in preparation method Sieve quinoline (1,10-Phenanthroline), 1,10 Phen pentaamino (1,10-phenanthroline-5-amine) phenol One kind in phthalein, thymol blue, fluorescein and oxyquinoline.In a more preferred embodiment, self-test colour developing molecule can be with Using 1,10 Phen, self-test colour developing is provided by providing 1,10 Phens.
Further, in a preferred embodiment of the invention, preparation method allows solid content control 20% or so, to obtain The planarization of best film forming and coating surface.
The above embodiment is the preferred case of the present invention, is not intended to limit protection scope of the present invention.

Claims (3)

1. a kind of method preparing the self-test anticorrosive paint containing nano-carrier, it is characterised in that include the following steps:
Step 1 prepares nano-carrier and configures the nano-carrier aqueous solution of proportional concentration;
The nano-carrier aqueous solution and self-test substance that show color are mixed to get the first mixed liquor by step 2 in proportion;
Step 3 obtains the second mixed liquor after first mixed liquor is carried out ultrasonic disperse;
Step 4 filters in removal second mixed liquor and obtains solid matter after unreacted solution, the solid matter is added Proportional third mixed liquor is matched after water;
The third mixed liquor and film forming matrix are mixed to get anticorrosive paint by step 5,
Wherein, the nano-carrier is arbitrary in graphene, nm-class boron nitride, nanoclay and layered double-hydroxide lamella Or mixtures thereof one kind,
The mass percent of the nano-carrier is 0.4%~4%,
The self-test substance that show color is thymol blue, fluorescein, oxyquinoline, 1,10 Phen (1,10- Phenanthroline), appointing in 1,10 Phen pentaaminos (1,10-phenanthroline-5-amine) and phenolphthalein Or mixtures thereof one kind of anticipating,
The film forming matrix is aqueous organic resin,
The aqueous organic resin is any one or its in aqueous polyurethane, water-based acrylic resin and aqueous epoxy resins Mixture,
Mass percent >=94% of the aqueous organic resin.
2. the method according to claim 1 for preparing the self-test anticorrosive paint containing nano-carrier, it is characterised in that:
Wherein, the mass percent of the self-test substance that show color is 0.2%~2%.
3. a kind of method preparing the self-test anticorrosive paint containing nano-carrier according to claim 1, it is characterised in that:
In the step 1, prepare nano-carrier and be configured to normal concentration be 1mg/ml~5mg/ml nano-carrier it is water-soluble Liquid;
In the step 2, by the nano-carrier solution and self-test substance that show color in mass ratio 0.9~3.5:0.3~1.8 Ratio be mixed to get the first mixed liquor;
In the step 4, the third mixed liquor for being 1mg/ml~5mg/ml is matched after the solid matter is added water.
CN201810256020.3A 2016-07-19 2016-07-19 Method for preparing self-detection anticorrosive paint containing nano-carrier Active CN108485495B (en)

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CN112175498A (en) * 2020-10-06 2021-01-05 青岛羚智涂料科技有限责任公司 Self-detection water-based self-repairing anticorrosive coating and preparation method thereof
CN112403409A (en) * 2020-10-06 2021-02-26 青岛羚智涂料科技有限责任公司 Self-detection capsule for water-based anticorrosive paint and preparation method thereof
CN116004093A (en) * 2022-12-26 2023-04-25 中国科学院福建物质结构研究所 Anticorrosive coating and preparation method thereof

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