CN110183569B - Metal corrosion early warning polymer coating material and preparation method thereof - Google Patents
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Abstract
The invention discloses a preparation method of a fluorescent early warning polymer coating for early corrosion of light metal, and belongs to the technical field of coating materials. The preparation method mainly comprises the following steps: firstly, a multi-acrylate random copolymer is synthesized, and then 8-hydroxyquinoline derivatives are used for carrying out quaternization modification on resin to finally prepare the photosensitive polymer. Coating the early corrosion fluorescent early warning coating on the surface of light metal such as magnesium, aluminum and the like to prepare an early corrosion fluorescent early warning coating; when corrosion occurs, the corrosion part can emit bright blue-green fluorescence under the irradiation of the ultraviolet lamp, thereby playing a role in early warning of corrosion. The early metal corrosion warning coating can detect and report early metal corrosion before any visible corrosion signs are displayed, and reminds maintainers of taking measures to avoid further corrosion of the metal, so that the early metal corrosion warning coating is a nondestructive early corrosion detection means.
Description
Technical Field
The invention belongs to the field of coating materials, and particularly relates to an early warning technology for detecting metal corrosion.
Background
With the requirement of light weight in industrial production and the trend of energy conservation and emission reduction under the increasingly tightened environmental protection policy of China, light metals represented by magnesium and aluminum alloy are increasingly applied to airplanes, ships, automobiles and 3C manufacturing. The problem of metal corrosion is more and more serious, and the economic loss caused by metal corrosion in China every year reaches 4 percent of the total value of national production. Therefore, corrosion protection has been a scientific field of intense research in all countries of the world. In production applications, metal surfaces are often provided with protective coatings. Over time, the protective coating may fail due to prolonged exposure to corrosive environments or mechanical damage, leaving portions of the metal surface susceptible to corrosion. Since coating failure is a process that ranges from quantitative to qualitative changes that often do not match inspection and maintenance cycles of the protected articles and structures. This is prone to the coating being intact at some stage or joint upon visual inspection, and in fact corrosion of the metal under the coating has occurred. In addition, corrosion often occurs at locations that are relatively difficult to monitor, and thus monitoring and repair can only be performed during periods when the service device is out of service or under overhaul. If corrosion cannot be found in time, the damage of the metal structure easily causes economic loss and safety accidents. Therefore, the corrosion position needs to be monitored in the initial stage of the corrosion of the metal material, so that people can find the damaged position of the material in time and evaluate the damaged position of the material, and reasonable measures are taken to carry out manual maintenance so as to prolong the service life of the material.
The preparation of polymer coating with fluorescent response to corrosion products is an effective means for detecting and early warning early corrosion of metals. The responsive polymer combines with the metal ions of the corrosion site to cause the corrosion site to fluoresce brightly visible to the naked eye under ultraviolet light, while the non-corroded site is non-fluorescent. Further, by observing the fluorescence intensity of the corroded site, the state of corrosion of the metal can be qualitatively judged. The early warning coating for metal corrosion can detect and report the early corrosion of metal before any visible corrosion signs are displayed, and reminds maintainers of taking measures to avoid further corrosion of the metal, and the characteristics of in-situ detection can be used for detecting a corrosion area without damage. Therefore, the development of the intelligent coating material with the self-warning function on the surface of the light metal has important research significance and application value.
Most of the existing Corrosion detection Coatings are prepared by directly adding some fluorescent molecules into polymer Coatings (andita Augustyniak, et., Progress in Organic Coatings,71(2011) 406-. And the basic performance of the coating is affected due to the reduction of the coating adhesion and barrier property caused by potential compatibility and other problems. These problems hinder the application of corrosion early detection coatings.
CN 106634422B discloses a high-molecular coating material for detecting metal corrosion, which is prepared by loading fluorescent molecules with pH response on a silica nano container and mixing the fluorescent molecules into a polymer coating. According to the invention, the using amount of fluorescent molecules is reduced through the silicon dioxide nano container, the problem of compatibility is solved to a certain extent, but the early warning of early corrosion is realized through the physical mixing of fluorescent substances and coating materials and the detection of the coating through the pH change of a corrosion part, so that the coating is easily interfered by external acid and alkali substances.
In addition, it is also an effective means to detect the corroded site by the change in color of the corroded site. The color-changing filler contained in the color-response early corrosion detection coating is combined with specific metal ions generated by corrosion of metal alloy or changes the pH value in the environment caused by corrosion to change the color of a corrosion part, so that the corrosion condition of metal can be monitored. (Zhang J, equivalent. Corroson Houston Tx,1999,55(10): 957-.
Disclosure of Invention
Aiming at the problems, the invention discloses a preparation method of a fluorescent early warning polymer coating for early corrosion of light metal, and belongs to the technical field of coating materials. The preparation method mainly comprises the following steps: firstly, a quadric acrylic random copolymer is synthesized, and then 8-hydroxyquinoline derivatives are used for carrying out quaternization modification on resin to finally prepare the photosensitive polymer. Coating the early corrosion fluorescent early warning coating on the surface of light metal such as magnesium, aluminum and the like to prepare an early corrosion fluorescent early warning coating; when corrosion occurs, the corrosion part can emit bright blue-green fluorescence under the irradiation of an ultraviolet lamp (300nm-400nm), thereby playing a role in early warning of corrosion. The early metal corrosion warning coating can detect and report early metal corrosion before any visible corrosion signs are displayed, and reminds maintainers of taking measures to avoid further corrosion of the metal, so that the early metal corrosion warning coating is a nondestructive early corrosion detection means.
The first purpose of the invention is to provide a preparation method of a fluorescent early warning polymer coating for early corrosion of light metal, which comprises the following steps:
firstly, preparing a copolymer by taking dimethylaminoethyl methacrylate, an acrylate monomer with the glass transition temperature Tg higher than 90 ℃, an acrylate monomer with the Tg lower than-40 ℃ and an acrylate monomer containing polar groups such as hydroxyl, amino and the like as raw materials;
and step two, carrying out quaternization reaction on the copolymer by using an 8-hydroxyquinoline derivative to obtain the metal corrosion early warning polymer coating material.
Specifically, in the first step, the proportion of the monomers participating in the reaction is adjusted, so that the Tg of the polymer is 37-100 ℃.
The monomer feeding can be adjusted according to the following formula so as to control the Tg of the polymer to be 37-100 ℃.
Wherein the Tg polymer has a glass transition temperature; wi participates in copolymerizing the mass fraction of each monomer; tg ofiThe glass transition temperature of the homopolymer of the monomer participating in the copolymerization.
Specifically, in the first step, the acrylate monomers with Tg higher than 90 ℃ comprise benzyl methacrylate, styrene and methyl methacrylate; the acrylate monomers with Tg lower than-40 ℃ comprise isooctyl acrylate and n-butyl acrylate; the acrylate monomer containing polar groups such as hydroxyl, amino and the like comprises hydroxyethyl acrylate.
Specifically, the amount of dimethylaminoethyl methacrylate used in the first step accounts for 1-25% of the mass fraction of the polymer.
Specifically, in the first step, the raw materials are dissolved in ethyl acetate, and a polymerization reaction is carried out under the initiation of an initiator, wherein the initiator is a conventional free radical initiator, and the initiator comprises azobisisobutyronitrile and dibenzoyl peroxide.
Specifically, in the second step, the modification rate of the 8-hydroxyquinoline derivative in the metal corrosion early warning polymer is 0.1-5%. The requirement of the target modification rate can be met by adjusting the molar ratio of the 8-hydroxyquinoline derivative to the dimethylaminoethyl methacrylate component in the copolymer to be 25-100%, the reaction time to be 12-24 h and the reaction temperature to be 60-90 ℃.
Specifically, in the second step, the copolymer is dissolved in N, N-dimethylformamide, and is subjected to quaternization reaction with the 8-hydroxyquinoline derivative in the presence of a catalyst and an acid-binding agent, after the reaction is finished, isocyano ethyl methacrylate diluted by the N, N-dimethylformamide is dropwise added for secondary reaction, and the metal corrosion early warning polymer coating material is obtained through precipitation.
The second purpose of the invention is to provide a metal corrosion early warning polymer coating material prepared by the method.
The third purpose of the invention is to provide a metal corrosion early warning polymer coating, which mainly comprises the steps of dissolving the metal corrosion early warning polymer coating material in a solvent and coating the solution on the metal surface.
Specifically, the solvent includes tetrahydrofuran, and is formulated into a polymer solution having a solid content of 20 wt%,
specifically, the coating method includes spray coating, dip coating, blade coating and electrophoretic deposition.
Specifically, the metals include magnesium alloys AZ31B, AZ91D, and AZ61, and aluminum alloys 2024, 4000, 5000, the surfaces of which need to be treated, including conventional phosphating, micro-arc oxidation, or silanization.
The prepared coating has better corrosion detection performance, and the corrosion part emits strong blue-green fluorescence under the irradiation of a 365nm portable ultraviolet lamp, thereby having good early warning effect on early corrosion.
The beneficial technical effects of the invention are as follows:
the invention synthesizes the photosensitive polymer through the chemical reaction of the fluorescent micromolecules and the polymer, and prepares the metal corrosion early warning polymer coating by taking the photosensitive polymer as the matrix resin. The protruding material can respond to magnesium ions and aluminum ions generated at early corrosion positions of light metal, so that bright fluorescence is emitted under ultraviolet light (300nm-400 nm). The early warning coating for the corrosion of the light metal can give a warning for the early corrosion of the metal before any visible corrosion signs are displayed, and reminds maintainers of taking measures to avoid further corrosion of the metal. In addition, the light metal corrosion early-stage fluorescence early-warning coating prepared by the invention adopts the photosensitive polymer with corrosion detection performance as the matrix resin and does not contain fluorescent micromolecule filler, so that the loss of the fluorescent micromolecules and the reduction of the basic performance of the coating caused by poor compatibility of the fluorescent micromolecules and a resin system are fundamentally avoided, and the prepared coating has good stability.
Drawings
FIG. 1 shows NMR spectra of copolymer PDHES, quaternized polymer QPDHES and metal corrosion warning polymer coating QUPDHES in example 1.
FIG. 2 shows the copolymer solution of example 2 with MgCl added in different (0-2) equivalents2The fluorescence spectrum of the sample.
FIG. 3 is a scanning electron microscope picture of an electrophoretically deposited coating of example 3 preparation of the coating.
Fig. 4 is an optical microscope picture under ultraviolet light before (a) and after (B) the aluminum alloy coating prepared in example 4 was soaked in 5% NaCl solution for 24 h.
Fig. 5 is a fluorescent microscope photograph of the scratch of the magnesium alloy coating prepared in example 4 before (a) and after (B) soaking in deionized water for 24 h.
Detailed Description
The invention is further illustrated below with reference to specific embodiments. It is to be understood that the present invention is not limited to the following embodiments, which are regarded as conventional methods unless otherwise specified. The materials are commercially available from the open literature unless otherwise specified.
Example 1:
(1) synthesis of copolymer: 4.71g (30mmol) of dimethylaminoethyl methacrylate (DMAEMA), 5.82g (58mmol) of styrene (St), 11.80g (64mmol) of isooctyl acrylate (EHA) and 4.64g (40mmol) of hydroxyethyl acrylate (HEA) are weighed and dissolved in 80mL of ethyl acetate, 0.886g of azobisisobutyronitrile as an initiator is added, nitrogen is introduced for removing oxygen for 30min, and the reaction is carried out for 24h at 80 ℃. After the reaction, most of the solvent was removed by rotary evaporation, and then Tetrahydrofuran (THF) was added to dilute the reaction solution, followed by repeated precipitation with petroleum ether to obtain a copolymer PDHES.
(2) The copolymer PDHES16g was dissolved in 80mL of N, N-Dimethylformamide (DMF), 1.03g (5.3mmol) of 5-chloromethyl-8-hydroxyquinoline (CHQ), 0.5g of sodium iodide as a catalyst, 3g of potassium carbonate as an acid-binding agent were added to the solution, the reaction was carried out at 80 ℃ for 24h, and the precipitation was repeated in diethyl ether to obtain a quaternized polymer QPDHES. Dissolving 8g of quaternized polymer in 30mL of ethyl acetate, dropwise adding 1.03g of isocyanoethyl methacrylate solution diluted by N, N-dimethylformamide, reacting at 50 ℃ for 8h, adding Tetrahydrofuran (THF) for dilution, and repeatedly precipitating by using petroleum ether to obtain a metal corrosion warning polymer coating material QUPDHES (quaternized modification rate of 3% at 52 ℃).
The results of the polymer are characterized by nuclear magnetic hydrogen spectrum, the results are shown in figure 1, and the successful synthesis of the metal corrosion early warning polymer coating material can be seen from the figure.
Preparation of a metal corrosion early warning polymer coating: and (3) dissolving a proper amount of the prepared metal corrosion early warning polymer coating material in tetrahydrofuran to prepare a polymer solution with the solid content of 20 wt%, then dip-coating the polymer solution on the surface of the magnesium alloy, and then irradiating for 2min by using a UV (ultraviolet) light curing machine to prepare the early corrosion fluorescent early warning coating.
Example 2:
(1) synthesis of copolymer: 4.71g (30mmol) of dimethylaminoethyl methacrylate (DMAEMA), 7.5g (75mmol) of styrene (St), 7.38g (40mmol) of isooctyl acrylate (EHA) and 5.8g (50mmol) of hydroxyethyl acrylate (HEA) are weighed and dissolved in 80mL of ethyl acetate, 0.886g of azobisisobutyronitrile as an initiator is added, nitrogen is introduced for removing oxygen for 30min, and the reaction is carried out for 24h at 80 ℃. After the reaction is finished, removing most of solvent by rotary evaporation, adding Tetrahydrofuran (THF) for dilution, and repeatedly precipitating by using petroleum ether to obtain a copolymer PDHES;
(2) dissolving 16g of copolymer PDHES in 80mL of N, N-Dimethylformamide (DMF), adding 0.5g (2.6mmol) of 5-chloromethyl-8-hydroxyquinoline (CHQ), 0.5g of sodium iodide as a catalyst and 3g of potassium carbonate as an acid-binding agent into the solution, reacting at 80 ℃ for 24h, and repeatedly precipitating in diethyl ether to obtain the quaternized polymer. Dissolving 8g of quaternized polymer in 30mL of ethyl acetate, dropwise adding 1.6g of isocyanoethyl methacrylate solution diluted by N, N-dimethylformamide, reacting at 50 ℃ for 8h, adding Tetrahydrofuran (THF) for dilution, and repeatedly precipitating by using petroleum ether to obtain a metal corrosion warning polymer coating material QUPDHES (quaternized modification rate of 64 ℃ Tg: 1.4%).
Adding 0.5mL, 1.0mL, 1.5mL and 2.0mL of magnesium chloride solution with the concentration of 1mmol/mL into 2mL of metal corrosion early warning polymer coating material ethanol solution with the concentration of 5mg/mL in sequence. The fluorescence responsivity of the polymer to magnesium ions is represented by a fluorescence spectrometer, and the result is shown in fig. 2, so that the fluorescence intensity of the metal corrosion early warning polymer coating material is increased along with the increase of the addition equivalent of the magnesium ions, and the prepared metal corrosion early warning polymer coating material has excellent fluorescence responsivity to the magnesium ions.
(3) Preparing a metal corrosion early warning polymer coating: and (3) dissolving a proper amount of the prepared metal corrosion early warning polymer coating material in tetrahydrofuran to prepare a polymer solution with the solid content of 20 wt%, then dip-coating the polymer solution on the surface of the magnesium alloy, and then irradiating for 2min by using a UV (ultraviolet) light curing machine to prepare the early corrosion fluorescent early warning coating.
Example 3:
(1) synthesis of copolymer: 6.28g (40mmol) of dimethylaminoethyl methacrylate (DMAEMA), 5.82g (58mmol) of styrene (St), 11.80g (64mmol) of isooctyl acrylate (EHA) and 4.64g (40mmol) of hydroxyethyl acrylate (HEA) were weighed out and dissolved in 80mL of ethyl acetate, 0.886g of azobisisobutyronitrile as an initiator was added, nitrogen was introduced to remove oxygen for 30min, and the reaction was carried out at 80 ℃ for 24 hours. After the reaction is finished, removing most of solvent by rotary evaporation, adding Tetrahydrofuran (THF) for dilution, and repeatedly precipitating by using petroleum ether to obtain a copolymer PDHES;
(2) copolymer PDHES16g was dissolved in 80mL of N, N-Dimethylformamide (DMF), 0.71g (3.5mmol) of 5-bromomethyl-8-hydroxyquinoline (BHQ) and 3g of potassium carbonate were added to the solution as an acid-binding agent, the reaction was carried out at 60 ℃ for 24h, and the precipitation was repeated in diethyl ether to give a quaternized polymer. Dissolving 8g of quaternized polymer in 30mL of ethyl acetate, dropwise adding 1.6g of isocyanoethyl methacrylate solution diluted by N, N-dimethylformamide, reacting at 50 ℃ for 8h, adding Tetrahydrofuran (THF) for dilution, and repeatedly precipitating by using petroleum ether to obtain a metal corrosion warning polymer coating material QUPDHES (quaternized modification rate of 5% at 38 ℃ Tg).
(3) Preparing an electrophoretic colloid solution: dissolving 5g of the metal corrosion early warning polymer coating material in 10mL of ethylene glycol monobutyl ether, adding 0.5g of lactic acid as a neutralizer, stirring at 60 ℃ for 0.5h to ensure that the reaction is complete, cooling to room temperature, and adding 0.15g of photoinitiator 1173. Deionized water was then added with stirring to prepare a colloidal solution having a concentration of 20 mg/mL. The colloidal particles have a particle size of about 300 nm.
(4) Preparing a metal corrosion early warning polymer coating: and (3) taking the colloidal solution as an electrodeposition solution, then taking AZ31B magnesium alloy as an anode and a platinum sheet as a counter electrode, controlling the deposition voltage to be 20V, carrying out electrophoretic deposition on the surface of the magnesium alloy for 2min to prepare an electrophoretic film, and then irradiating for 2min by using a UV curing machine to prepare the metal corrosion early warning polymer coating. Fig. 4 is a scanning electron microscope picture of the coating layer prepared. The prepared coating is relatively flat and compact as can be seen from the figure.
Example 4:
(1) synthesis of copolymer: 6.28g (40mmol) of dimethylaminoethyl methacrylate (DMAEMA), 5.80g (58mmol) of Methyl Methacrylate (MMA), 11.80g (64mmol) of isooctyl acrylate (EHA) and 4.64g (40mmol) of hydroxyethyl acrylate (HEA) are weighed and dissolved in 80mL of ethyl acetate, 0.886g of azobisisobutyronitrile initiator is added, nitrogen is introduced for removing oxygen for 30min, and the reaction is carried out for 24h at 80 ℃. After the reaction, most of the solvent was removed by rotary evaporation, and then Tetrahydrofuran (THF) was added to dilute the reaction solution, followed by repeated precipitation with petroleum ether to obtain a copolymer PDHES.
(2) The copolymer PDHES16g is dissolved in 80mL of N, N-Dimethylformamide (DMF), 0.5g (2.6mmol) of 5-chloromethyl-8-hydroxyquinoline (CHQ), 0.25g of sodium iodide as a catalyst and 1.5g of potassium carbonate as an acid-binding agent are added to the solution, the reaction is carried out at 80 ℃ for 12h, and the precipitation is repeated in diethyl ether, so as to obtain the quaternary ammonium polymer. Dissolving 8g of quaternized polymer in 30mL of ethyl acetate, dropwise adding 1.2g of isocyanoethyl methacrylate solution diluted by N, N-dimethylformamide, reacting at 50 ℃ for 8h, adding Tetrahydrofuran (THF) for dilution, and repeatedly precipitating by using petroleum ether to obtain a metal corrosion warning polymer coating material QUPDHES (quaternized modification rate of 1.7% at 41 ℃).
(3) Preparing an electrophoretic colloid solution: dissolving 5g of the metal corrosion early warning polymer coating material in 10mL of ethylene glycol monobutyl ether, adding 0.5g of lactic acid as a neutralizer, stirring at 60 ℃ for 0.5h to ensure that the reaction is complete, cooling to room temperature, and adding 0.15g of photoinitiator 1173. Deionized water was then added with stirring to prepare a colloidal solution having a concentration of 20 mg/mL.
(4) Preparing a metal corrosion early warning polymer coating: and (3) taking the colloidal solution as an electrodeposition solution, then taking an aluminum alloy as a cathode and a platinum sheet as a counter electrode, controlling the deposition voltage to be 20V, depositing for 2min to prepare an electrophoretic film on the surface of the magnesium alloy through electrophoretic deposition, and then irradiating for 2min by using a UV (ultraviolet) curing machine to prepare the metal corrosion early warning polymer coating.
In order to examine the corrosion early warning performance of the prepared coating, the aluminum alloy coated with the coating is immersed in a 5% NaCl solution for 24 hours, and an optical microscope is adopted to observe whether the defective part of the coating generates fluorescence response under the irradiation of 365nm ultraviolet light, wherein the result is shown in figure 5. It can be seen from fig. 4A that almost no fluorescence is generated at the coating defect under the ultraviolet lamp before the sample is soaked, while in fig. 4B, the coating defect has strong blue-green fluorescence under the ultraviolet light in the sample soaked by the NaCl solution. This shows that the prepared functional coating has good detection effect on corrosion of magnesium alloy
Example 5:
(1) synthesis of copolymer: 4.71g (30mmol) of dimethylaminoethyl methacrylate (DMAEMA), 5.82g (58mmol) of Methyl Methacrylate (MMA), 8.19g (64mmol) of n-Butyl Acrylate (BA) and 4.64g (40mmol) of hydroxyethyl acrylate (HEA) are weighed and dissolved in 80mL of ethyl acetate, 0.886g of azobisisobutyronitrile initiator is added, nitrogen is introduced for removing oxygen for 30min, and the reaction is carried out for 24h at 80 ℃. After the reaction is finished, most of the solvent is removed by rotary evaporation, Tetrahydrofuran (THF) is added for dilution, and petroleum ether is used for repeated precipitation to obtain a standby copolymer PDHES.
(2) Dissolving 16g of copolymer PDHES in 80mL of N, N-Dimethylformamide (DMF), adding 0.5g (2.6mmol) of 5-chloromethyl-8-hydroxyquinoline (CHQ), 0.5g of sodium iodide as a catalyst and 3g of potassium carbonate as an acid-binding agent into the solution, reacting at 90 ℃ for 24 hours, and repeatedly precipitating in diethyl ether to obtain the quaternized modified polymer.
(3) Preparing a metal corrosion early warning polymer coating: dissolving the quaternized modified polymer in tetrahydrofuran to prepare a polymer solution with the solid content of 20 wt%, adding blocked diisocyanate, carrying out dip coating on the surface of the magnesium alloy, and curing for 1h at 150 ℃ by using an oven to prepare a metal corrosion early warning polymer coating QUPDHES (the quaternized modification rate is 1.9% at 55 ℃).
In order to further test the corrosion early warning effect of the coating, a nick is scribed on the magnesium alloy sheet coated with the functional coating by using a cutter, the magnesium alloy sheet is placed into deionized water to be soaked for 24 hours, and the fluorescence change before and after the nick is corroded is observed by using a front fluorescence microscope, and the result is shown in fig. 5. As can be seen from fig. 5A, the coating showed very weak fluorescence at the scratch, while fig. 5B showed strong green fluorescence at the scratch. The prepared functional coating can effectively early warn the corrosion of the magnesium alloy.
Example 6:
(1) synthesis of copolymer: 4.71g (30mmol) of dimethylaminoethyl methacrylate (DMAEMA), 10g (58mmol) of Benzyl Methacrylate (BMA), 8.19g (64mmol) of n-Butyl Acrylate (BA) and 3.96g (40mmol) of hydroxyethyl acrylate (HEA) are weighed and dissolved in 80mL of ethyl acetate, 0.886g of azodiisobutyronitrile as an initiator is added, nitrogen is introduced for removing oxygen for 30min, and the reaction is carried out for 24h at 80 ℃. And (3) after the reaction is finished, removing most of the solvent by rotary evaporation, adding Tetrahydrofuran (THF) for dilution, and repeatedly precipitating by using petroleum ether to obtain the copolymer.
(2) 16g of the copolymer was dissolved in 80mL of N, N-Dimethylformamide (DMF), 0.1g (0.5mmol) of 5-chloromethyl-8-hydroxyquinoline (CHQ), 0.5g of sodium iodide as a catalyst, 3g of potassium carbonate as an acid-binding agent were added to the solution, and the mixture was reacted at 90 ℃ for 12 hours, followed by repeated precipitation in diethyl ether to obtain a quaternary ammonium polymer. Dissolving 8g of quaternized polymer in 30mL of ethyl acetate, dropwise adding 1.6g of isocyanoethyl methacrylate solution diluted by N, N-dimethylformamide, reacting at 50 ℃ for 8h, adding Tetrahydrofuran (THF) for dilution, and repeatedly precipitating by using petroleum ether to obtain a metal corrosion warning polymer coating material QUPDHES (quaternized modification rate of 0.2% at 60 ℃) which is a metal corrosion warning polymer coating material.
(3) Preparing a metal corrosion early warning polymer coating: dissolving a proper amount of metal corrosion early warning polymer coating material in tetrahydrofuran to prepare a polymer solution with the solid content of 25 wt%, and then irradiating the surface of the aluminum alloy for 2min by using a UV (ultraviolet) photo-curing machine through a dip coating method to prepare the metal corrosion early warning polymer coating.
The above is only a preferred embodiment of the present invention, and it should be noted that: it will be apparent to those skilled in the art that various modifications and adaptations can be made without departing from the principles of the invention and these are intended to be within the scope of the invention.
Claims (10)
1. A preparation method of a metal corrosion early warning polymer coating material is characterized by mainly comprising the following steps:
firstly, preparing a copolymer by taking dimethylaminoethyl methacrylate, an acrylate monomer with the glass transition temperature Tg higher than 90 ℃, an acrylate monomer with the Tg lower than-40 ℃ and an acrylate monomer containing hydroxyl and amino polar groups as raw materials;
and step two, carrying out quaternization reaction on the copolymer by using an 8-hydroxyquinoline derivative to obtain the metal corrosion early warning polymer coating material.
2. The preparation method of the metal corrosion early warning polymer coating material according to claim 1, wherein the proportion of the monomers participating in the reaction in the first step is adjusted to make the Tg of the polymer 37-100 ℃.
3. The preparation method of the metal corrosion early warning polymer coating material according to claim 1, wherein in the first step, the acrylate monomers with Tg higher than 90 ℃ comprise benzyl methacrylate, styrene and methyl methacrylate; the acrylate monomers with Tg lower than-40 ℃ comprise isooctyl acrylate and n-butyl acrylate; the acrylate monomer containing hydroxyl and amino polar groups comprises hydroxyethyl acrylate.
4. The preparation method of the metal corrosion early warning polymer coating material according to claim 1, wherein the amount of dimethylaminoethyl methacrylate in the first step is 1-25% of the mass fraction of the raw material monomers.
5. The preparation method of the metal corrosion early warning polymer coating material according to claim 1, wherein in the first step, the raw materials are dissolved in ethyl acetate, and polymerization reaction is carried out under initiation of an initiator, wherein the initiator is a conventional free radical initiator, and the initiator comprises azobisisobutyronitrile and dibenzoyl peroxide.
6. The method for preparing a metal corrosion early warning polymer coating material according to claim 1, wherein in the second step, the modification rate of the 8-hydroxyquinoline derivative in the metal corrosion early warning polymer is 0.1-5%.
7. The preparation method of the metal corrosion early warning polymer coating material according to claim 1, wherein in the second step, the copolymer is dissolved in N, N-dimethylformamide, and is subjected to quaternization reaction with the 8-hydroxyquinoline derivative in the presence of a catalyst and an acid-binding agent, after the reaction is finished, isocyanoethyl methacrylate diluted by N, N-dimethylformamide is added dropwise for secondary reaction, and the metal corrosion early warning polymer coating material is obtained through precipitation.
8. The method for preparing a metal corrosion early warning polymer coating material according to claim 7, wherein the catalyst comprises sodium iodide; the acid-binding agent comprises potassium carbonate; the 8-hydroxyquinoline derivatives include 5-chloromethyl-8-hydroxyquinoline and 5-bromomethyl-8-hydroxyquinoline.
9. A metal corrosion early warning polymer coating material, which is characterized by being prepared according to the method of any one of claims 1 to 8.
10. A metal corrosion early warning polymer coating, which is characterized in that the metal corrosion early warning polymer coating material of claim 9 is dissolved in tetrahydrofuran and coated on the metal surface.
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