CN110183569A - A kind of metal erosion early warning polymer coating materials and preparation method thereof - Google Patents
A kind of metal erosion early warning polymer coating materials and preparation method thereof Download PDFInfo
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Abstract
The preparation method for corroding fluorescence early warning polymer coating the invention discloses a kind of light metal early stage, belongs to coating material technical field.The preparation method mainly includes the following contents: a kind of multicomponent methacrylate random copolymer has been synthesized first, it is quaternised modified to resin progress using 8-hydroxyquinoline derivative later, and photosensitive polymer is finally prepared.It is painted on the light metal surfaces such as magnesium, aluminium preparation early stage corrosion fluorescence early warning coating；When corroding generation, corrosion location can issue bright blue-green fluorescent under ultraviolet light irradiation, to play the forewarning function to early stage corrosion.This metal erosion early warning coating can detect and report the early stage corrosion of metal before any visible signs of corrosion is shown, remind service personnel to take measures, avoid further corroding for metal, be a kind of lossless early stage Corrosion monitoring means.
Description
Technical field
The invention belongs to coating material fields, and in particular to one kind is for detecting metal erosion early warning technology.
Background technique
Energy-saving and emission-reduction becomes under the environmental protection policy increasingly tightened with requirement light-weighted in industrial production and China
Gesture is more and more applied in aircraft, ship, automobile and 3C manufacture using magnesium, aluminium alloy as the light metal of representative.Metal erosion
The problem of it is increasingly severe, China every year because caused by metal erosion economic loss reached the 4% of gross national product.Cause
This, all the time, corrosion protection is all the scientific domain of countries in the world primary study.In production application, metal surface is often
Protective coating can be applied.Over time, protective coating may be due to being exposed to corrosive environment or mechanical damage for a long time
And fail, make part-metallic surface be easy to corrode.Since coating failure is a process from quantitative change to qualitative change, and this variation
Often do not matched that with the inspection of protected object part and structure, maintenance cycle.This be easy for appearing in some stage or node into
Coating is intact when row visual inspection, and actually corrosion phenomenon has occurred for metal under coating.In addition, corrosion occurs often in relatively
It is not easy the position monitored, consequently only that just can be monitored and repair during the break-off of military service device or overhaul.If rotten
Erosion cannot be found that the destruction of metal structure be easy to cause economic loss and safety accident in time.Therefore, in metallic material corrosion
The germinating stage just need to be monitored corrosive attack position, make people timely find to comment at material breakage and to it
Estimate, to take reasonable measure to carry out manual maintenance, to extend the service life of material.
By preparing the polymer coating that there is fluorescence response to corrosion product, to detect the early stage with early warning metal
Corrosion is the effective means that solves the above problems.The polymer of responsiveness makes corrosion location exist in conjunction with the metal ion of corrosion location
Macroscopic bright fluorescence is issued under ultraviolet light, without the position unstressed configuration corroded.In addition, passing through observation corrosion portion
The fluorescence intensity of position, can qualitatively judge metal corrosion condition.This metal erosion early warning coating can it is any can
Before the signs of corrosion seen is shown, detects and report the early stage corrosion of metal, remind service personnel to take measures, avoid metal
It further corrodes, and the characteristics of its in situ detection lossless can detect corrosion area.Therefore, in light metal surface
Development has important research significance and application value with the smart coat material from warning function.
Existing Corrosion monitoring coating is mostly that some fluorescent molecules are directly added the (Anita in polymer coating
Augustyniak,etal.,Progress in Organic Coatings,71(2011)406–412；J.Zhang,et
Al., Corrosion, 55 (1999) 957-967.), these fluorescent molecules are added directly into coating, and easily generation migration causes glimmering
The loss of optical molecule simultaneously is easy to play interaction with ambient enviroment and fail.And the problems such as due to potential compatibility, is easy
The reduction for leading to paint adhesion and barrier property influences the basic performance of coating.These problems hinder corrosion early detection and apply
The application of layer.
106634422 B of CN discloses a kind of fluorescent molecule by silica nanometer container payload with pH response,
It mixes in polymer coating, is prepared for a kind of for detecting the polymeric coating material of metal erosion.The invention passes through titanium dioxide
Silicon nano container reduces the usage amount of fluorescent molecule, solves the problems, such as compatibility to a certain extent, but substantially or logical
The physical mixed by fluorescent material and coating material is crossed, and detecting coating is to realize by corrosion location pH variation to early stage corruption
The early warning of erosion is easy the interference by extraneous acid-base material.
In addition, carrying out detection to corrosion location by the variation of corrosion location color is also a kind of effective means.Color is rung
Answer the discoloration filler contained in type early stage Corrosion monitoring coating, with metal alloy corrosion generate special metal ions binding or because
The variation of pH value can monitor corrosion of metal situation to make corrosion location color change in environment caused by corroding.
(Zhang J,etal.Corrosion Houston Tx,1999,55(10):957-967；Raps D,etal.Corrosion
Science, 2009,51 (5): 1012-1021) still, compared with carrying out early warning to corrosion location by fluorescence, pass through corrosion portion
The detection sensitivity of the variation early warning corrosion of position color is low, often when early stage, corrosion had occurred and that, the color of corrosion location according to
Do not change so.
Summary of the invention
In view of the above-mentioned problems, corroding the preparation side of fluorescence early warning polymer coating the invention discloses a kind of light metal early stage
Method belongs to coating material technical field.The preparation method mainly includes the following contents: synthesized first a kind of quaternary acrylic acid without
Copolymer is advised, it is quaternised modified to resin progress using 8-hydroxyquinoline derivative later, photosensitive polymer is finally prepared.
It is painted on the light metal surfaces such as magnesium, aluminium preparation early stage corrosion fluorescence early warning coating；When corroding generation, corrosion location is in purple
Outer lamp (300nm-400nm) irradiation is lower to issue bright blue-green fluorescent, to play the forewarning function to early stage corrosion.This
Kind metal erosion early warning coating can detect before any visible signs of corrosion is shown and report that the early stage of metal is rotten
Erosion reminds service personnel to take measures, avoids further corroding for metal, is a kind of lossless early stage Corrosion monitoring means.
Corrode the preparation side of fluorescence early warning polymer coating the first purpose of the invention is to provide a kind of light metal early stage
Method, which comprises
The first step, with dimethylaminoethyl methacrylate, glass transition temperature Tg is higher than 90 DEG C of esters of acrylic acid
Monomer and Tg are lower than -40 DEG C of acrylic ester monomer, and the acrylate list containing hydroxyl, amido isopolarity group
Body prepares copolymer as raw material；
Second step carries out quaternization reaction to above-mentioned copolymer with 8-hydroxyquinoline derivative, obtains metal erosion early warning
Polymer coating materials.
Specifically, adjusting monomer described in the first step participates in the ratio of reaction, makes 37~100 DEG C of polymer Tg.
Can according to the following formula, adjusting monomeric charge makes polymer Tg control at 37~100 DEG C.
The glass transition temperature of Tg polymer in formula；Wi participates in the mass fraction for being copolymerized each monomer；TgiParticipate in copolymerization
The glass transition temperature of monomer homopolymers.
Specifically, acrylic ester monomer of the Tg described in the first step higher than 90 DEG C includes methacrylic acid Bian ester, benzene second
Alkene, methyl methacrylate；Acrylic ester monomer of the Tg lower than -40 DEG C includes Isooctyl acrylate monomer, the positive fourth of acrylic acid
Ester；The acrylate monomer containing hydroxyl, amido isopolarity group includes hydroxy-ethyl acrylate.
Specifically, the dosage of dimethylaminoethyl methacrylate described in the first step account for polymer quality score 1~
25%.
Specifically, in ethyl acetate polymerization reaction, institute occur under the initiation of initiator for dissolution of raw material described in the first step
Stating initiator is conventional radical initiators, and the initiator includes azodiisobutyronitrile, dibenzoyl peroxide.
Specifically, the degree of modification of 8-hydroxyquinoline derivative is in the polymer of metal erosion early warning described in second step
0.1%~5%.It can be by adjusting dimethylaminoethyl methacrylate component in 8-hydroxyquinoline derivative and copolymer
Molar ratio be 25%~100%, reaction time 12~for 24 hours with reaction temperature at 60~90 DEG C to reach wanting for target degree of modification
It asks.
Specifically, copolymer is dissolved in n,N-Dimethylformamide in second step, in the presence of catalyst and acid binding agent
Quaternization reaction is carried out with 8-hydroxyquinoline derivative, the diluted metering system of n,N-Dimethylformamide is added dropwise after reaction
Sour isocyano group ethyl ester secondary response, is precipitated, and metal erosion early warning polymer coating materials are obtained.
A second object of the present invention is to provide a kind of metal erosion early warning polymer coatings that the above method is prepared
Material.
It mainly include by above-mentioned metal third object of the present invention is to provide a kind of metal erosion early warning polymer coating
Corrode the dissolution of early warning polymer coating materials in a solvent, is painted on metal surface.
Specifically, the solvent includes tetrahydrofuran, and is configured to the polymer solution of solid content 20wt%,
Specifically, the mode of coating includes spraying, dip-coating, blade coating and electrophoretic deposition.
Specifically, metal includes magnesium alloy AZ31B, AZ91D and AZ61, and aluminium alloy 2024,4000,5000, surface needs
It will be by processing, including conventional phosphorating treatment, micro-arc oxidation treatment or silanization treatment.
Prepared coating has preferable Corrosion monitoring performance, under the irradiation of 365nm hand-held ultraviolet lamp, corrosion location
Strong blue-green fluorescent is issued, good early warning effect is played to early stage corrosion.
The present invention is beneficial to be had the technical effect that
The present invention passes through the chemical reaction of fluorescent small molecule and polymer, has synthesized photosensitive polymer, and as base
Body resin prepares metal erosion early warning polymer coating.The protrusion material can to light metal early stage corrosion location generate magnesium from
Son, aluminium ion respond, to issue bright fluorescence at ultraviolet light (300nm-400nm).This light metal corrosion is early
Phase early warning coating can issue early warning to the early stage corrosion of metal, remind maintenance before any visible signs of corrosion is shown
Personnel take measures, and avoid further corroding for metal.In addition, light metal corrosion early stage fluorescence early warning prepared by the present invention applies
Layer is free of fluorescent small molecule filler, fundamentally using the photosensitive polymer with Corrosion monitoring performance as matrix resin
Avoid the poor compatibility due to fluorescent small molecule and resin system, the loss and coating basic performance of caused fluorescent small molecule
Decline, prepared coating is with good stability.
Detailed description of the invention
Fig. 1 is that copolymer p DHES, the quaternary ammonium polymer QPDHES and metal erosion early warning polymer in embodiment 1 are applied
Layer material QUPDHES nuclear magnetic resonance spectroscopy.
Fig. 2 is the MgCl that different (0~2) equivalents are added in 2 copolymer solution of embodiment2Fluorescence spectrum afterwards.
Fig. 3 is the scanning electron microscope diagram piece of the electrophoretic deposition coating of 3 prepares coating of embodiment.
Fig. 4 be embodiment 4 prepare aluminium alloy covered impregnated for 24 hours in 5%NaCl solution before (A) afterwards (B), under ultraviolet light
Optical microscope picture.
Fig. 5 be embodiment 4 prepared by magnesium alloy coating impregnate for 24 hours in deionized water before (A) afterwards (B), at scratch
Fluorescence microscope picture.
Specific embodiment
Below in conjunction with specific implementation case, the invention will be further elaborated.It should be understood that the present invention is not limited to following realities
Case is applied, the method is accordingly to be regarded as conventional method unless otherwise instructed.The material unless otherwise instructed can be from open business
Approach obtains.
Embodiment 1:
(1) 4.71g (30mmol) dimethylaminoethyl acrylate methyl ammonia ethyl ester (DMAEMA), 5.82g the synthesis of copolymer: are weighed
(58mmol) styrene (St), 11.80g (64mmol) Isooctyl acrylate monomer (EHA), 4.64g (40mmol) hydroxy-ethyl acrylate
(HEA) it is dissolved in 80mL ethyl acetate, adds initiator azodiisobutyronitrile 0.886g, lead to nitrogen deoxygenation 30min, at 80 DEG C
Reaction is for 24 hours.Revolving removes most of solvent after reaction, and tetrahydrofuran (THF) dilution is added, is sunk repeatedly using petroleum ether
It forms sediment, obtains copolymer p DHES.
(2) copolymer p DHES16g is dissolved in 80mL n,N-Dimethylformamide (DMF), then is added into solution
1.03g (5.3mmol) 5- chloromethyl -8-hydroxyquinoline (CHQ), 0.5g sodium iodide are used as catalyst, 3g potassium carbonate and tie up acid
Agent, reacts for 24 hours at 80 DEG C, and the repeated precipitation in ether obtains quaternary ammonium polymer QPDHES.8g quaternary ammonium polymer is molten
1.03g isocyanatoethyl of the solution in 30mL ethyl acetate, after n,N-Dimethylformamide dilution is added dropwise
Solution reacts 8h at 50 DEG C, and tetrahydrofuran (THF) dilution is added, using petroleum ether repeated precipitation, obtains metal erosion early warning
Polymer coating materials QUPDHES (Tg=52 DEG C of quaternised modified rate 3%).
It is just characterized by result of the nucleus magnetic hydrogen spectrum to polymer, as a result as shown in Figure 1, as can be seen from the figure successfully
Metal erosion early warning polymer coating materials are synthesized.
A kind of preparation of metal erosion early warning polymer coating: appropriate above-mentioned preparation metal erosion early warning polymer coating is taken
Material is dissolved in tetrahydrofuran, is configured to the polymer solution of solid content 20wt%, and then dip-coating is in Mg alloy surface, with
2min is irradiated using UV photo solidification machine afterwards, early stage corrosion fluorescence early warning coating is prepared.
Embodiment 2:
(1) 4.71g (30mmol) dimethylaminoethyl acrylate methyl ammonia ethyl ester (DMAEMA), 7.5g the synthesis of copolymer: are weighed
(75mmol) styrene (St), 7.38g (40mmol) Isooctyl acrylate monomer (EHA), 5.8g (50mmol) hydroxy-ethyl acrylate
(HEA) it is dissolved in 80mL ethyl acetate, adds initiator azodiisobutyronitrile 0.886g, lead to nitrogen deoxygenation 30min, at 80 DEG C
Reaction is for 24 hours.Revolving removes most of solvent after reaction, and tetrahydrofuran (THF) dilution is added, is sunk repeatedly using petroleum ether
It forms sediment, obtains copolymer p DHES；
(2) copolymer p DHES 16g is dissolved in 80mL n,N-Dimethylformamide (DMF), then is added into solution
0.5g (2.6mmol) 5- chloromethyl -8-hydroxyquinoline (CHQ), 0.5g sodium iodide are used as catalyst, 3g potassium carbonate and tie up acid
Agent, reacts for 24 hours at 80 DEG C, and the repeated precipitation in ether obtains quaternary ammonium polymer.8g quaternary ammonium polymer is dissolved in
In 30mL ethyl acetate, the 1.6g isocyanatoethyl solution after n,N-Dimethylformamide dilutes is added dropwise,
8h is reacted at 50 DEG C, tetrahydrofuran (THF) dilution is added, and using petroleum ether repeated precipitation, obtains metal erosion early warning polymerization
Object coating material QUPDHES (Tg=64 DEG C of quaternised modified rate 1.4%).
In the metal erosion early warning polymer coating materials ethanol solution for being 5mg/mL to 2mL concentration, sequentially add
0.5mL, 1.0mL, 1.5mL, 2.0mL concentration are the magnesium chloride solution of 1mmol/mL.Polymer pair is characterized by Fluorescence Spectrometer
The fluorescence response of magnesium ion, as a result as shown in Figure 2, it can be seen that metal erosion early warning polymer coating materials add with magnesium ion
The increase of sovolin amount, fluorescence intensity increase therewith, thus the metal erosion early warning polymer coating materials being prepared to magnesium from
Son has excellent fluorescence response.
(3) preparation of metal erosion early warning polymer coating: appropriate above-mentioned preparation metal erosion early warning polymer coating is taken
Material is dissolved in tetrahydrofuran, is configured to the polymer solution of solid content 20wt%, and then dip-coating is in Mg alloy surface, with
2min is irradiated using UV photo solidification machine afterwards, early stage corrosion fluorescence early warning coating is prepared.
Embodiment 3:
(1) 6.28g (40mmol) dimethylaminoethyl acrylate methyl ammonia ethyl ester (DMAEMA), 5.82g the synthesis of copolymer: are weighed
(58mmol) styrene (St), 11.80g (64mmol) Isooctyl acrylate monomer (EHA), 4.64g (40mmol) hydroxy-ethyl acrylate
(HEA) it is dissolved in 80mL ethyl acetate, adds initiator azodiisobutyronitrile 0.886g, lead to nitrogen deoxygenation 30min, at 80 DEG C
Reaction is for 24 hours.Revolving removes most of solvent after reaction, and tetrahydrofuran (THF) dilution is added, is sunk repeatedly using petroleum ether
It forms sediment, obtains copolymer p DHES；
(2) copolymer p DHES16g is dissolved in 80mL n,N-Dimethylformamide (DMF), then is added into solution
0.71g (3.5mmol) 5- bromomethyl -8-hydroxyquinoline (BHQ), 3g potassium carbonate as acid binding agent, reacted at 60 DEG C for 24 hours,
Repeated precipitation in ether, obtains quaternary ammonium polymer.8g quaternary ammonium polymer is dissolved in 30mL ethyl acetate, is added dropwise
1.6g isocyanatoethyl solution after n,N-Dimethylformamide dilution, reacts 8h at 50 DEG C, and tetrahydro is added
Furans (THF) dilution, using petroleum ether repeated precipitation, obtains metal erosion early warning polymer coating materials QUPDHES (Tg=38
DEG C quaternised modified rate 5%).
(3) preparation of electrophoresis colloidal solution: the above-mentioned metal erosion early warning polymer coating materials of 5g are taken, 10mL second is dissolved in
In glycol monobutyl ether, 0.5g lactic acid is added as neutralizer, and stirring 0.5h makes its fully reacting at 60 DEG C, is cooled to room temperature and adds
Enter 0.15g photoinitiator 1173.It then is kept stirring addition deionized water, it is 20mg/mL colloidal solution that concentration, which is prepared,.Glue
The particle size of body particle is about 300nm.
(4) preparation of metal erosion early warning polymer coating: above-mentioned colloidal solution is electrodeposit liquid, then with AZ31B magnesium
Alloy is anode, and platinized platinum is to electrode, and control deposition voltage is 20V, and sedimentation time is 2min in Mg alloy surface electrophoretic deposition
Electrocoating film is prepared, then 2min is irradiated using UV photo solidification machine, metal erosion early warning polymer coating is prepared.Fig. 4 is system
The scanning electron microscope diagram piece of standby coating.As can be seen from the figure prepared coating is more smooth, fine and close.
Embodiment 4:
(1) 6.28g (40mmol) dimethylaminoethyl acrylate methyl ammonia ethyl ester (DMAEMA), 5.80g the synthesis of copolymer: are weighed
(58mmol) methyl methacrylate (MMA), 11.80g (64mmol) Isooctyl acrylate monomer (EHA), 4.64g (40mmol) propylene
Sour hydroxyl ethyl ester (HEA) is dissolved in 80mL ethyl acetate, adds initiator azodiisobutyronitrile 0.886g, leads to nitrogen deoxygenation
30min reacts for 24 hours at 80 DEG C.Revolving removes most of solvent after reaction, and tetrahydrofuran (THF) dilution is added, uses stone
Oily ether repeated precipitation obtains copolymer p DHES.
(2) copolymer p DHES 16g is dissolved in 80mL n,N-Dimethylformamide (DMF), then is added into solution
0.5g (2.6mmol) 5- chloromethyl -8-hydroxyquinoline (CHQ), 0.25g sodium iodide are used as and tie up as catalyst, 1.5g potassium carbonate
Sour agent reacts 12h at 80 DEG C, and the repeated precipitation in ether obtains quaternary ammonium polymer.8g quaternary ammonium polymer is dissolved in
In 30mL ethyl acetate, the 1.2g isocyanatoethyl solution after n,N-Dimethylformamide dilutes is added dropwise,
8h is reacted at 50 DEG C, tetrahydrofuran (THF) dilution is added, and using petroleum ether repeated precipitation, obtains metal erosion early warning polymerization
Object coating material QUPDHES (Tg=41 DEG C of quaternised modified rate 1.7%).
(3) preparation of electrophoresis colloidal solution: the above-mentioned metal erosion early warning polymer coating materials of 5g are taken, 10mL second is dissolved in
In glycol monobutyl ether, 0.5g lactic acid is added as neutralizer, and stirring 0.5h makes its fully reacting at 60 DEG C, is cooled to room temperature and adds
Enter 0.15g photoinitiator 1173.It then is kept stirring addition deionized water, it is 20mg/mL colloidal solution that concentration, which is prepared,.
(4) preparation of metal erosion early warning polymer coating: above-mentioned colloidal solution is electrodeposit liquid, is then with aluminium alloy
Cathode, platinized platinum are to electrode, and control deposition voltage is 20V, and sedimentation time is 2min in Mg alloy surface electrophoretic deposition preparation electricity
Swimming film, then irradiates 2min using UV photo solidification machine, metal erosion early warning polymer coating is prepared.
For the corrosion early warning performance for examining or check prepared coating, the aluminium alloy for being coated with coating immerses in 5%NaCl solution
It impregnates for 24 hours, using optical microphotograph sem observation holiday position under 365nm ultraviolet light, if generate fluorescence response, knot
Fruit is as shown in Figure 5.As can be seen from Figure 4A, it before sample immersion, is generated in the UV lamp almost without fluorescence at holiday,
And in Fig. 4 B, by the sample that NaCl solution is impregnated, there is strong blue-green fluorescent at holiday position under ultraviolet light.This says
Bright, prepared functional coating has good detection effect to the corrosion of magnesium alloy
Embodiment 5:
(1) 4.71g (30mmol) dimethylaminoethyl acrylate methyl ammonia ethyl ester (DMAEMA), 5.82g the synthesis of copolymer: are weighed
(58mmol) methyl methacrylate (MMA), 8.19g (64mmol) n-butyl acrylate (BA), 4.64g (40mmol) acrylic acid
Hydroxyl ethyl ester (HEA) is dissolved in 80mL ethyl acetate, adds initiator azodiisobutyronitrile 0.886g, leads to nitrogen deoxygenation 30min,
It is reacted for 24 hours at 80 DEG C.Revolving removes most of solvent after reaction, and tetrahydrofuran (THF) dilution is added, anti-using petroleum ether
Multiple precipitating, obtains spare copolymer p DHES.
(2) copolymer p DHES 16g is dissolved in 80mL n,N-Dimethylformamide (DMF), then is added into solution
0.5g (2.6mmol) 5- chloromethyl -8-hydroxyquinoline (CHQ), 0.5g sodium iodide are used as catalyst, 3g potassium carbonate and tie up acid
Agent, reacts for 24 hours at 90 DEG C, and the repeated precipitation in ether obtains quaternised modified polymer.
(3) preparation of metal erosion early warning polymer coating: above-mentioned quaternised modified polymer is taken, tetrahydrofuran is dissolved in
In, it is configured to the polymer solution of solid content 20wt%, closing diisocyanate is added, then passes through dip-coating in Mg alloy surface
Then metal erosion early warning polymer coating QUPDHES (Tg=55 DEG C of season is prepared in 150 DEG C of solidification 1h using baking oven in method
Ammonium degree of modification 1.9%).
For the corrosion early warning effect of further testing coating, by the standardized road of magnesium alloy plate cutter of coating functions coating
Scratch, and be put into deionized water and impregnate for 24 hours, corrode front and back change in fluorescence at its scratch of fluorescence microscope using just setting,
As a result as shown in Figure 5.As can be seen from Figure 5A, at scratch, coating shows very faint fluorescence, and occurs at Fig. 5 B scratch strong
Strong green fluorescence.This absolutely proves that prepared functional coating effectively can play forewarning function to the corrosion of magnesium alloy.
Embodiment 6:
(1) 4.71g (30mmol) dimethylaminoethyl acrylate methyl ammonia ethyl ester (DMAEMA), 10g the synthesis of copolymer: are weighed
(58mmol) methacrylic acid Bian ester (BMA), 8.19g (64mmol) n-butyl acrylate (BA), 3.96g (40mmol) acrylic acid
Hydroxyl ethyl ester (HEA) is dissolved in 80mL ethyl acetate, adds initiator azodiisobutyronitrile 0.886g, leads to nitrogen deoxygenation 30min,
It is reacted for 24 hours at 80 DEG C.Revolving removes most of solvent after reaction, and tetrahydrofuran (THF) dilution is added, anti-using petroleum ether
Multiple precipitating, obtains copolymer.
(2) copolymer 1 6g is dissolved in 80mL n,N-Dimethylformamide (DMF), then 0.1g is added into solution
(0.5mmol) 5- chloromethyl -8-hydroxyquinoline (CHQ), 0.5g sodium iodide as catalyst, 3g potassium carbonate as acid binding agent,
12h is reacted at 90 DEG C, the repeated precipitation in ether obtains quaternary ammonium polymer.8g quaternary ammonium polymer is dissolved in 30mL second
In acetoacetic ester, the 1.6g isocyanatoethyl solution after n,N-Dimethylformamide dilutes is added dropwise, at 50 DEG C
Lower reaction 8h is added tetrahydrofuran (THF) dilution, using petroleum ether repeated precipitation, obtains metal erosion early warning polymer coating
Material QUPDHES (Tg=60 DEG C of quaternised modified rate 0.2%).
(3) preparation of metal erosion early warning polymer coating: taking appropriate metal erosion early warning polymer coating materials, dissolution
In tetrahydrofuran, it is configured to the polymer solution of solid content 25wt%, is then then made in aluminum alloy surface by dip coating
2min is irradiated with UV photo solidification machine, metal erosion early warning polymer coating is prepared.
Described is only the preferred embodiment of the present invention, it should be pointed out that: those skilled in the art are come
It says, various improvements and modifications may be made without departing from the principle of the present invention, these improvements and modifications also should be regarded as
Protection scope of the present invention.
Claims (10)
1. a kind of preparation method of metal erosion early warning polymer coating materials, which is characterized in that mainly pass through following steps:
The first step, with dimethylaminoethyl methacrylate, glass transition temperature Tg is higher than 90 DEG C of acrylic ester monomer,
And Tg is lower than -40 DEG C of acrylic ester monomer, and contains the acrylate monomer conduct of hydroxyl, amido isopolarity group
Raw material prepares copolymer；
Second step carries out quaternization reaction to above-mentioned copolymer with 8-hydroxyquinoline derivative, obtains metal erosion early warning polymerization
Object coating material.
2. a kind of preparation method of metal erosion early warning polymer coating materials according to claim 1, which is characterized in that
Adjusting monomer described in the first step participates in the ratio of reaction, makes 37~100 DEG C of polymer Tg.
3. a kind of preparation method of metal erosion early warning polymer coating materials according to claim 1, which is characterized in that
Acrylic ester monomer of the Tg described in the first step higher than 90 DEG C includes benzyl methacrylate, styrene, methyl methacrylate
Ester；Acrylic ester monomer of the Tg lower than -40 DEG C includes Isooctyl acrylate monomer, n-butyl acrylate；It is described containing hydroxyl,
The acrylate monomer of amido isopolarity group includes hydroxy-ethyl acrylate.
4. a kind of preparation method of metal erosion early warning polymer coating materials according to claim 1, which is characterized in that
The dosage of dimethylaminoethyl methacrylate described in the first step accounts for the 1~25% of starting monomer mass fraction.
5. a kind of preparation method of metal erosion early warning polymer coating materials according to claim 1, which is characterized in that
In ethyl acetate polymerization reaction occurs under the initiation of initiator for dissolution of raw material described in the first step, and the initiator is conventional
Radical initiator, the initiator include azodiisobutyronitrile, dibenzoyl peroxide.
6. a kind of preparation method of metal erosion early warning polymer coating materials according to claim 1, which is characterized in that
The degree of modification of 8-hydroxyquinoline derivative is 0.1%~5% in the polymer of metal erosion early warning described in second step.
7. a kind of preparation method of metal erosion early warning polymer coating materials according to claim 1, which is characterized in that the
Copolymer is dissolved in n,N-Dimethylformamide in two steps, in the presence of catalyst and acid binding agent with 8-hydroxyquinoline derivative
Quaternization reaction is carried out, the diluted isocyanatoethyl secondary counter of n,N-Dimethylformamide is added dropwise after reaction
It answers, is precipitated, obtain metal erosion early warning polymer coating materials.
8. a kind of preparation method of metal erosion early warning polymer coating materials according to claim 7, which is characterized in that institute
Stating catalyst includes sodium iodide；Acid binding agent includes potassium carbonate；8-hydroxyquinoline derivative include 5- chloromethyl -8-hydroxyquinoline,
5- bromomethyl -8-hydroxyquinoline.
9. a kind of metal erosion early warning polymer coating materials, which is characterized in that according to any side of claim 1~8
Method preparation gained.
10. a kind of metal erosion early warning polymer coating, which is characterized in that gather metal erosion early warning as claimed in claim 9
It closes object coating material to be dissolved in tetrahydrofuran, is painted on metal surface.
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| CN111455286A (en) * | 2020-04-09 | 2020-07-28 | 宁波万冠熔模铸造有限公司 | Marine fitting with corrosion indicator layer and method of making same |
| CN112940275A (en) * | 2021-02-08 | 2021-06-11 | 北京石油化工学院 | Preparation method of metal organic framework compound material |
| CN113413839A (en) * | 2021-07-07 | 2021-09-21 | 西南交通大学 | Salt response polyaniline microcapsule, self-warning coating and preparation method |
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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 |
| WO2018048461A1 (en) * | 2016-09-06 | 2018-03-15 | The Arizona Board Of Regents On Behalf Of The University Of Arizona | Electrochemical detection of corrosion and corrosion rates of metal in molten salts at high temperatures |
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| CN106189771A (en) * | 2016-07-19 | 2016-12-07 | 上海理工大学 | A kind of Autonomous test anticorrosive paint containing nano-carrier and its preparation method and application |
| WO2018048461A1 (en) * | 2016-09-06 | 2018-03-15 | The Arizona Board Of Regents On Behalf Of The University Of Arizona | Electrochemical detection of corrosion and corrosion rates of metal in molten salts at high temperatures |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN111455286A (en) * | 2020-04-09 | 2020-07-28 | 宁波万冠熔模铸造有限公司 | Marine fitting with corrosion indicator layer and method of making same |
| CN111455286B (en) * | 2020-04-09 | 2021-04-06 | 宁波万冠熔模铸造有限公司 | Marine fitting with corrosion indicator layer and method of making same |
| CN112940275A (en) * | 2021-02-08 | 2021-06-11 | 北京石油化工学院 | Preparation method of metal organic framework compound material |
| CN112940275B (en) * | 2021-02-08 | 2022-05-20 | 北京石油化工学院 | Preparation method of metal organic framework compound material |
| CN113413839A (en) * | 2021-07-07 | 2021-09-21 | 西南交通大学 | Salt response polyaniline microcapsule, self-warning coating and preparation method |
| CN113413839B (en) * | 2021-07-07 | 2022-04-05 | 西南交通大学 | Salt response polyaniline microcapsule, self-warning coating and preparation method |
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