CN105885611A - Polymer metallic copper anticorrosive coating and preparation method thereof - Google Patents
Polymer metallic copper anticorrosive coating and preparation method thereof Download PDFInfo
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- CN105885611A CN105885611A CN201610403361.XA CN201610403361A CN105885611A CN 105885611 A CN105885611 A CN 105885611A CN 201610403361 A CN201610403361 A CN 201610403361A CN 105885611 A CN105885611 A CN 105885611A
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D151/00—Coating compositions based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers
- C09D151/10—Coating compositions based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers grafted on to inorganic materials
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F292/00—Macromolecular compounds obtained by polymerising monomers on to inorganic materials
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/08—Anti-corrosive paints
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Abstract
The invention discloses a polymer metallic copper anticorrosive coating. The coating is prepared from, by weight, 0.7-1 part of potassium zirconium carbonate, 0.8-1 part of 2,4-tetrahydroglyoxaline diketone, 0.1-0.3 part of butyl benzyl phthalate, 10-14 parts of vinyl trimethoxy silane, 200-300 parts of 1.8-2g/l citric acid solution, 13-17 parts of silane coupling agent KB5103, 100-110 parts of tetraethoxysilane, 30-37 parts of hexafluorobutyl acrylate, 0.1-0.14 part of azodiisobutyronitrile, 5-7 parts of 20-25% ammonium hydroxide, 4-5 parts of ferroferric oxide, 1-2 parts of dodecyl trimethyl ammonium chloride, 3-4 parts of ethylparaben, 0.1-0.2 part of difenoconazole and 1-2 parts of sodium polyacrylate. Hybridized coating surfaces different in different morphology can be formed, the coating surfaces of different structures are combined with a low-surface-energy ethylene group exposed out, and the coating has a super-hydrophobic character.
Description
Technical field
The present invention relates to technical field of metal anti-corrosion, particularly relate to a kind of polymer metallic copper corrosion-inhibiting coating and preparation method thereof.
Background technology
In recent years; enhancing along with people's environmental consciousness; traditional protection by metallic coating or surface treatment method face a severe challenge; as though plating can form all hook, fine and close protective layer; but electroplating process can produce substantial amounts of waste water, waste gas and waste residue; wherein contain the extremely toxic substance such as heavy metal chromium, cyanate, bring serious threat to environment;And the change treatment technology of metal surface, phosphating process produce sediment and phosphate easily cause the oxygen enrichment of water quality, the pollution etc. of water quality is also needed to seek new surface treatment method by nitrite, heavy metal ion.In recent years; new eco-friendly surface-coating technology arises at the historic moment; bionical selfreparing corrosion-inhibiting coating such as mimic biology body self-repair function principle; self-assembled monolayer technology; super-hydrophobic film technology; it is noted that owing to super-hydrophobic film technology shows great using value in the lossless conveying of anticorrosion inhibition, self-cleaning surface, frost resistance, Drag Reduction and microfluid, biotechnology field and causes the extensive concern of people, the research in this field is the most active.Super-hydrophobic film technology be according to water droplet can on super hydrophobic surface free rolling phenomenon-" lotus leaf effect " and a kind of metal surface treating method of proposing.Micro nano structure and top layer matter thereof at lotus leaf surface impart surface super hydrophobic performance jointly.Super hydrophobic surface micro nano structure can improve static contact angle, makes drop be difficult to penetrate into micro-nano coarse structure, causes the physical isolation of metal and Korrosionsmedium, reach etch-proof purpose.Metal surface treatment technology based on super-hydrophobic film technology is widely used in improving the decay resistance of various metals material, exactly because the automatically cleaning that also super-hydrophobic film is unique and Corrosion Protection, becomes one the most promising protecting metallic surface method；
Affecting the infiltrating key factor of the surface of solids is surface free energy, and when surface free energy reduces, hydrophobic performance will be increased.But, even if having the surface of smooth solid of minimum surface energy and the contact angle also only 119 ° of water, therefore, only super hydrophobic surface can not be obtained by fall low-surface-energy.
Existing research shows, builds super hydrophobic surface mainly by two approach, and the first modifies low-surface energy substance at the substrate surface of raw sugar;It two is to build at hydrophobic surface to have the micro nano structure of certain raw sugar degree, and according to these two approach, scientists has developed the method for a lot of structure super hydrophobic surface, constructed the super hydrophobic surface of different surfaces structure.
The etching problem faced in the environment in view of metal material, and super hydrophobic surface is one of the most promising protecting metallic surface method；The purpose of the present invention is exactly to study the anti-corrosive metal coating of a kind of super hydrophobic surface.
Summary of the invention
The object of the invention is contemplated to make up the defect of prior art, it is provided that a kind of polymer metallic copper corrosion-inhibiting coating and preparation method thereof.
The present invention is achieved by the following technical solutions:
A kind of polymer metallic copper corrosion-inhibiting coating, this coating is made up of the raw material of following weight parts:
Potassium zirconium carbonate 0.7-1,2,4-imidazolinedione 0.8-1, BBP(Butyl Benzyl Phthalate 0.1-0.3, the citric acid solution 200-300 of vinyltrimethoxy silane 10-14,1.8-2g/l, silane coupler KBM510313-17, tetraethyl orthosilicate 100-110, hexafluorobutyl acrylate 30-37, the ammonia 5-7 of azodiisobutyronitrile 0.1-0.14,20-25%, ferroso-ferric oxide 4-5, Dodecyl trimethyl ammonium chloride 1-2, ethyl hydroxybenzoate 3-4, Difenoconazole 0.1-0.2, sodium polyacrylate 1-2.
The preparation method of the polymer metallic copper corrosion-inhibiting coating described in a kind of claim 1, comprises the following steps:
(1) above-mentioned ferroso-ferric oxide is joined in the citric acid solution of 1.8-2g/l, ultrasonic disperse 1.7-2 hour, sucking filtration, by filter cake absolute ethanol washing 2-3 time, it is vacuum dried 10-20 minute at 76-80 DEG C, obtains sour modification ferroso-ferric oxide；
(2) above-mentioned Dodecyl trimethyl ammonium chloride is joined in the deionized water of its weight 18-20 times, stir, add above-mentioned potassium zirconium carbonate, acid modification ferroso-ferric oxide, 100-200 rev/min is stirred 20-30 minute, rise high-temperature and be 60-70 DEG C, be incubated standby, obtain composite dispersion liquid；
(3) above-mentioned sodium polyacrylate is joined in the deionized water of its weight 17-20 times, stir, add the 5-7% of above-mentioned tetraethyl orthosilicate weight, rise high-temperature and be 50-60 DEG C, insulated and stirred 20-30 minute, obtain polymer modification Ludox；
(4) above-mentioned composite dispersion liquid is joined in its weight 370-400 times, 30-35% ethanol solution, ultrasonic 20-30 minute, add above-mentioned silane coupler KBM5103, remaining tetraethyl orthosilicate, 700-1000 rev/min of stirring is reacted 6-7 hour, mixes with above-mentioned polymer modification Ludox, stirs, sucking filtration, by filter cake absolute ethanol washing 2-3 time, it is vacuum dried 20-25 hour at 100-110 DEG C, obtains ethenyl blocking composite；
(5) above-mentioned ethenyl blocking composite is joined in the dimethylformamide of its weight 100-105 times, ultrasonic 40-50 minute, it is passed through nitrogen, add above-mentioned Difenoconazole, hexafluorobutyl acrylate, azodiisobutyronitrile, react 5-7 hour at 70-80 DEG C, be cooled to room temperature, sucking filtration, filter cake dimethylformamide is washed 3-4 time, is vacuum dried 10-14 hour at 80-90 DEG C, obtains fluorination composite；
(6) above-mentioned fluorination composite is joined in the ethanol solution of its weight 15-17 times, 95-97%, ultrasonic disperse 10-20 minute, add and remain each raw material, stir, put into the copper sheet cleaned up, soak 20-26 hour, take out, be dried at 60-65 DEG C, obtain described coating.
The invention have the advantage that the present invention is initially with citric acid modification magnetic Fe 304 nanoparticle, it can be made the most molten with silane coupler KBM5103 as aqueous favoring, then by silane coupler KBM5103 and the hydrolysis of tetraethyl orthosilicate, introduce the siloxanes of ethenyl blocking on ferroso-ferric oxide surface, provide vinyl active group for graft polymerization reaction.Hexafluorobutyl acrylate passes through glycerol polymerization with the ferroso-ferric oxide/siloxanes compound particle of ethenyl blocking, fluoropolymer is formed on compound particle surface, then fluoropolymer compound particle is joined in silanol liquid, reduce the surface energy of coating, improve the hydrophobic performance of coating；This silanol liquid with vinyltrimethoxy silane as presoma, ammonia is as catalyst, vinyltrimethoxy silane first occurs hydrolysis to generate silanol, dehydrogenation the most in the basic conditions, other silicon atomic core are started nucleophilic attack, condensation reaction is occurred to form Si-0-Si key, and along with dehydration or dealcoholysis, nucleation, growth is progressively assembled at copper-based surfaces, ultimately form the hybrid coating surface of various different-shape, the coating surface of different structure combines the vinyl group of exposed low-surface-energy, jointly imparts coating and has superhydrophobic characteristic.Present invention adds multiple polymers, effectively raise the surface strength of finished product coating, improve peeling resistance.
Detailed description of the invention
A kind of polymer metallic copper corrosion-inhibiting coating, this coating is made up of the raw material of following weight parts:
Potassium zirconium carbonate 0.7,2,4 imidazolinediones 0.8, BBP(Butyl Benzyl Phthalate 0.1, vinyltrimethoxy silane 10, the citric acid solution 200 of 1.8g/l, silane coupler KBM510313, tetraethyl orthosilicate 100, hexafluorobutyl acrylate 30, the ammonia 5 of azodiisobutyronitrile 0.1,20%, ferroso-ferric oxide 4, Dodecyl trimethyl ammonium chloride 1, ethyl hydroxybenzoate 3, Difenoconazole 0.1, sodium polyacrylate 1.
The preparation method of the polymer metallic copper corrosion-inhibiting coating described in a kind of claim 1, comprises the following steps:
(1) above-mentioned ferroso-ferric oxide is joined in the citric acid solution of 1.8g/l, ultrasonic disperse 1.7 hours, sucking filtration, by filter cake absolute ethanol washing 2 times, it is vacuum dried 10 minutes at 76 DEG C, obtains sour modification ferroso-ferric oxide；
(2) above-mentioned Dodecyl trimethyl ammonium chloride being joined in the deionized water of its weight 18 times, stir, add above-mentioned potassium zirconium carbonate, acid modification ferroso-ferric oxide, 100 revs/min are stirred 20 minutes, and rising high-temperature is 60 DEG C, is incubated standby, obtains composite dispersion liquid；
(3) being joined by above-mentioned sodium polyacrylate in the deionized water of its weight 17 times, stir, add the 5% of above-mentioned tetraethyl orthosilicate weight, rising high-temperature is 50 DEG C, and insulated and stirred 20 minutes obtains polymer modification Ludox；
(4) above-mentioned composite dispersion liquid is joined in its weight 370 times, the ethanol solution of 30%, ultrasonic 20 minutes, add above-mentioned silane coupler KBM5103, remaining tetraethyl orthosilicate, 700 revs/min of stirrings are reacted 6 hours, mix with above-mentioned polymer modification Ludox, stir, sucking filtration, by filter cake absolute ethanol washing 2 times, it is vacuum dried 20 hours at 100 DEG C, obtains ethenyl blocking composite；
(5) above-mentioned ethenyl blocking composite is joined in the dimethylformamide of its weight 100 times, ultrasonic 40 minutes, it is passed through nitrogen, add above-mentioned Difenoconazole, hexafluorobutyl acrylate, azodiisobutyronitrile, react 5 hours at 70 DEG C, be cooled to room temperature, sucking filtration, filter cake dimethylformamide is washed 3 times, be vacuum dried 10 hours at 80 DEG C, obtain fluorination composite；
(6) above-mentioned fluorination composite is joined its weight 15 times, 95% ethanol solution in, ultrasonic disperse 10 minutes, add and remain each raw material, stir, put into the copper sheet cleaned up, soaks 20 hours, take out, dry at 60 DEG C, obtain described coating.
Performance test:
Copper sheet coating of the present invention processed is placed more than 12 months at normal temperature laboratory, still has superhydrophobic characteristic；
The copper sheet substrate cleaned up is hydrophilic (contact angle is less than 90 °), and the static contact angle to water is 85 ± 1.1；The coating of the present invention is rendered as super-hydrophobicity, and its contact angle is 154 ± 1.5；
The solution of different pH is dropped in the coating surface of the present invention, stand 30 minutes, measure its contact angle again, it is that 2-12 is in the range of this at pH, contact angle is both greater than 150 °, illustrate that strong acid, highly basic have good acid-proof alkaline on superhydrophobic surface structure and chemical composition thereof almost without impact, the coating that this composite particles is formed.
Claims (2)
1. a polymer metallic copper corrosion-inhibiting coating, it is characterised in that this coating is made up of the raw material of following weight parts:
Potassium zirconium carbonate 0.7-1,2,4-imidazolinedione 0.8-1, BBP(Butyl Benzyl Phthalate 0.1-0.3, the citric acid solution 200-300 of vinyltrimethoxy silane 10-14,1.8-2g/l, silane coupler KBM510313-17, tetraethyl orthosilicate 100-110, hexafluorobutyl acrylate 30-37, the ammonia 5-7 of azodiisobutyronitrile 0.1-0.14,20-25%, ferroso-ferric oxide 4-5, Dodecyl trimethyl ammonium chloride 1-2, ethyl hydroxybenzoate 3-4, Difenoconazole 0.1-0.2, sodium polyacrylate 1-2.
2. the preparation method of the polymer metallic copper corrosion-inhibiting coating described in a claim 1, it is characterised in that comprise the following steps:
(1) above-mentioned ferroso-ferric oxide is joined in the citric acid solution of 1.8-2g/l, ultrasonic disperse 1.7-2 hour, sucking filtration, by filter cake absolute ethanol washing 2-3 time, it is vacuum dried 10-20 minute at 76-80 DEG C, obtains sour modification ferroso-ferric oxide；
(2) above-mentioned Dodecyl trimethyl ammonium chloride is joined in the deionized water of its weight 18-20 times, stir, add above-mentioned potassium zirconium carbonate, acid modification ferroso-ferric oxide, 100-200 rev/min is stirred 20-30 minute, rise high-temperature and be 60-70 DEG C, be incubated standby, obtain composite dispersion liquid；
(3) above-mentioned sodium polyacrylate is joined in the deionized water of its weight 17-20 times, stir, add the 5-7% of above-mentioned tetraethyl orthosilicate weight, rise high-temperature and be 50-60 DEG C, insulated and stirred 20-30 minute, obtain polymer modification Ludox；
(4) above-mentioned composite dispersion liquid is joined in its weight 370-400 times, 30-35% ethanol solution, ultrasonic 20-30 minute, add above-mentioned silane coupler KBM5103, remaining tetraethyl orthosilicate, 700-1000 rev/min of stirring is reacted 6-7 hour, mixes with above-mentioned polymer modification Ludox, stirs, sucking filtration, by filter cake absolute ethanol washing 2-3 time, it is vacuum dried 20-25 hour at 100-110 DEG C, obtains ethenyl blocking composite；
(5) above-mentioned ethenyl blocking composite is joined in the dimethylformamide of its weight 100-105 times, ultrasonic 40-50 minute, it is passed through nitrogen, add above-mentioned Difenoconazole, hexafluorobutyl acrylate, azodiisobutyronitrile, react 5-7 hour at 70-80 DEG C, be cooled to room temperature, sucking filtration, filter cake dimethylformamide is washed 3-4 time, is vacuum dried 10-14 hour at 80-90 DEG C, obtains fluorination composite；
(6) above-mentioned fluorination composite is joined in the ethanol solution of its weight 15-17 times, 95-97%, ultrasonic disperse 10-20 minute, add and remain each raw material, stir, put into the copper sheet cleaned up, soak 20-26 hour, take out, be dried at 60-65 DEG C, obtain described coating.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106520019A (en) * | 2016-10-18 | 2017-03-22 | 铜陵市肆得科技有限责任公司 | Epoxy metal antirust adhesive and preparation method thereof |
| CN106800856A (en) * | 2016-12-20 | 2017-06-06 | 铜陵市经纬流体科技有限公司 | A kind of anti-corrosion hybrid microspheres grafting silicon composite coating and preparation method thereof |
| CN106835102A (en) * | 2016-12-30 | 2017-06-13 | 张庆 | A kind of nano oxidized cerium modified organic-inorganic silane passivating film |
| CN106835106A (en) * | 2016-12-30 | 2017-06-13 | 张庆 | A kind of good shitosan Inorganic whisker passivating film of film forming |
| CN106835107A (en) * | 2016-12-30 | 2017-06-13 | 张庆 | A kind of antimicrobial form organic-inorganic environmental protection composite passivation film |
| CN106835101A (en) * | 2016-12-30 | 2017-06-13 | 张庆 | A kind of modified Nano titanium compound is combined super-hydrophobic passivating film |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105419626A (en) * | 2015-10-28 | 2016-03-23 | 天长市润达金属防锈助剂有限公司 | Macromolecule aluminum alloy anti-corrosion Czochralski collosol and preparation method thereof |
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2016
- 2016-06-08 CN CN201610403361.XA patent/CN105885611A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105419626A (en) * | 2015-10-28 | 2016-03-23 | 天长市润达金属防锈助剂有限公司 | Macromolecule aluminum alloy anti-corrosion Czochralski collosol and preparation method thereof |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106520019A (en) * | 2016-10-18 | 2017-03-22 | 铜陵市肆得科技有限责任公司 | Epoxy metal antirust adhesive and preparation method thereof |
| CN106800856A (en) * | 2016-12-20 | 2017-06-06 | 铜陵市经纬流体科技有限公司 | A kind of anti-corrosion hybrid microspheres grafting silicon composite coating and preparation method thereof |
| CN106835102A (en) * | 2016-12-30 | 2017-06-13 | 张庆 | A kind of nano oxidized cerium modified organic-inorganic silane passivating film |
| CN106835106A (en) * | 2016-12-30 | 2017-06-13 | 张庆 | A kind of good shitosan Inorganic whisker passivating film of film forming |
| CN106835107A (en) * | 2016-12-30 | 2017-06-13 | 张庆 | A kind of antimicrobial form organic-inorganic environmental protection composite passivation film |
| CN106835101A (en) * | 2016-12-30 | 2017-06-13 | 张庆 | A kind of modified Nano titanium compound is combined super-hydrophobic passivating film |
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Application publication date: 20160824 |