CN105907225A - Metallic copper anti-corrosion titanium sol coating and preparation method thereof - Google Patents
Metallic copper anti-corrosion titanium sol coating and preparation method thereof Download PDFInfo
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- CN105907225A CN105907225A CN201610420320.1A CN201610420320A CN105907225A CN 105907225 A CN105907225 A CN 105907225A CN 201610420320 A CN201610420320 A CN 201610420320A CN 105907225 A CN105907225 A CN 105907225A
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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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- C—CHEMISTRY; METALLURGY
- 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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- 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
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/60—Additives non-macromolecular
- C09D7/61—Additives non-macromolecular inorganic
Abstract
The invention discloses a metallic copper anti-corrosion titanium sol coating. The coating is prepared from, by weight, 4-7 parts of tetrabutyl titanate, 0.2-0.4 part of triethyl citrate, 0.7-1 part of magnesium stearate, 10-14 parts of vinyl trimethoxy silane, 200-300 parts of 1.8-2 g/l citric acid solution, 13-17 parts of silane coupling agent KBM 5103, 100-110 parts of tetraethylortho silicate, 30-37 parts of hexafluorobutyl acrylate, 0.1-0.14 part of azodiisobutyronitrile, 7-9 parts of 20-25% ammonia water, 4-5 parts of ferroferric oxide, 1-2 parts of amino trimethylene phosphonic acid, 0.6-1 part of alkylolamide, 2-3 parts of hydrolytic polymaleic anhydride and 3-4 parts of diphenyl silanediol. Hybrid coating surfaces in various shapes can be formed, and the coating surfaces of different structures are combined with low-surface-energy vinyl groups exposed outside so that the coating can have super-hydrophobicity.
Description
Technical field
The present invention relates to technical field of metal anti-corrosion, particularly relate to a kind of metallic copper anticorrosion titanium collosol 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 metallic copper anticorrosion titanium collosol coating and preparation method thereof.
The present invention is achieved by the following technical solutions:
A kind of metallic copper anticorrosion titanium collosol coating, this coating is made up of the raw material of following weight parts:
Butyl titanate 4-7, triethyl citrate 0.2-0.4, magnesium stearate 0.7-1, 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 ammoniacal liquor 7-9 of azodiisobutyronitrile 0.1-0.14,20-25%, ferroso-ferric oxide 4-5, ATMP 1-2, alkylolamides 0.6-1, HPMA 2-3, diphenyl silanediol 3-4.
The preparation method of the metallic copper anticorrosion titanium collosol coating described in a kind of claim 1, comprises the following steps:
(1) being joined by said hydrolyzed HPMA in the deionized water of its weight 10-13 times, stir, add alkylolamides, rise high-temperature and be 70-80 DEG C, add above-mentioned ferroso-ferric oxide, insulated and stirred to water is done, and obtains pretreatment ferroso-ferric oxide；
(2) above-mentioned pretreatment ferroso-ferric oxide is joined in the citric acid solution of 1.8-2g/l, ultrasonic disperse 1.7-2 hour, suction 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；
(3) above-mentioned butyl titanate is joined in its weight 10-13 times, 70-75% ethanol solution, stir, add diphenyl silanediol, rise high-temperature and be 60-70 DEG C, insulated and stirred 20-30 minute, add the 10-12% of the weights of ammonia of above-mentioned 20-25%, stirring mixing 30-40 minute, obtain modification sol；
(4) ferroso-ferric oxide is modified in above-mentioned acid and join in its weight 370-400 times, 30-35% ethanol solution, ultrasonic 20-30 minute, add above-mentioned silane coupler KBM5103, tetraethyl orthosilicate, 700-1000 rev/min of stirring is reacted 6-7 hour, mixes with above-mentioned modification sol, and 100-200 rev/min is stirred 3-4 minute, suction 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, adds aforesaid propylene acid hexafluoro butyl ester, azodiisobutyronitrile, react 5-7 hour at 70-80 DEG C, mix with above-mentioned magnesium stearate, stir, be cooled to room temperature, suction 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 nano particle, 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, ammoniacal liquor 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.The titanium colloidal sol that the present invention adds can effectively improve filler grain dispersiveness in the polymer, improves the stability_intensity of coating.
Detailed description of the invention
A kind of metallic copper anticorrosion titanium collosol coating, this coating is made up of the raw material of following weight parts:
Butyl titanate 4, triethyl citrate 0.2, magnesium stearate 0.7, vinyltrimethoxy silane 10, the citric acid solution 200 of 1.8g/l, silane coupler KBM510313, tetraethyl orthosilicate 100, hexafluorobutyl acrylate 30, the ammoniacal liquor 7 of azodiisobutyronitrile 0.1,20%, ferroso-ferric oxide 4, ATMP 1, alkylolamides 0.6, HPMA 2, diphenyl silanediol 3.
The preparation method of the metallic copper anticorrosion titanium collosol coating described in a kind of claim 1, comprises the following steps:
(1) being joined by said hydrolyzed HPMA in the deionized water of its weight 10 times, stir, add alkylolamides, rising high-temperature is 70 DEG C, adds above-mentioned ferroso-ferric oxide, and insulated and stirred to water is done, and obtains pretreatment ferroso-ferric oxide；
(2) above-mentioned pretreatment ferroso-ferric oxide is joined in the citric acid solution of 1.8g/l, ultrasonic disperse 1.7 hours, suction 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；
(3) above-mentioned butyl titanate is joined in its weight 10 times, the ethanol solution of 70%, stir, add diphenyl silanediol, rise high-temperature be 60 DEG C, insulated and stirred 20 minutes, add above-mentioned 20% weights of ammonia 10%, stirring mixing 30 minutes, obtains modification sol；
(4) ferroso-ferric oxide is modified in above-mentioned acid and join in its weight 370 times, the ethanol solution of 30%, ultrasonic 20 minutes, add above-mentioned silane coupler KBM5103, tetraethyl orthosilicate, 700 revs/min of stirrings are reacted 6 hours, mix with above-mentioned modification sol, and 100 revs/min are stirred 3 minutes, suction 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, adds aforesaid propylene acid hexafluoro butyl ester, azodiisobutyronitrile, react 5 hours at 70 DEG C, mix with above-mentioned magnesium stearate, stir, be cooled to room temperature, suction 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 metallic copper anticorrosion titanium collosol coating, it is characterised in that this coating is made up of the raw material of following weight parts:
Butyl titanate 4-7, triethyl citrate 0.2-0.4, magnesium stearate 0.7-1, 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 ammoniacal liquor 7-9 of azodiisobutyronitrile 0.1-0.14,20-25%, ferroso-ferric oxide 4-5, ATMP 1-2, alkylolamides 0.6-1, HPMA 2-3, diphenyl silanediol 3-4.
2. the preparation method of the metallic copper anticorrosion titanium collosol coating described in a claim 1, it is characterised in that comprise the following steps:
(1) being joined by said hydrolyzed HPMA in the deionized water of its weight 10-13 times, stir, add alkylolamides, rise high-temperature and be 70-80 DEG C, add above-mentioned ferroso-ferric oxide, insulated and stirred to water is done, and obtains pretreatment ferroso-ferric oxide；
(2) above-mentioned pretreatment ferroso-ferric oxide is joined in the citric acid solution of 1.8-2g/l, ultrasonic disperse 1.7-2 hour, suction 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；
(3) above-mentioned butyl titanate is joined in its weight 10-13 times, 70-75% ethanol solution, stir, add diphenyl silanediol, rise high-temperature and be 60-70 DEG C, insulated and stirred 20-30 minute, add the 10-12% of the weights of ammonia of above-mentioned 20-25%, stirring mixing 30-40 minute, obtain modification sol；
(4) ferroso-ferric oxide is modified in above-mentioned acid and join in its weight 370-400 times, 30-35% ethanol solution, ultrasonic 20-30 minute, add above-mentioned silane coupler KBM5103, tetraethyl orthosilicate, 700-1000 rev/min of stirring is reacted 6-7 hour, mixes with above-mentioned modification sol, and 100-200 rev/min is stirred 3-4 minute, suction 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, adds aforesaid propylene acid hexafluoro butyl ester, azodiisobutyronitrile, react 5-7 hour at 70-80 DEG C, mix with above-mentioned magnesium stearate, stir, be cooled to room temperature, suction 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 (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN106700811A (en) * | 2016-12-20 | 2017-05-24 | 铜陵市经纬流体科技有限公司 | Aerogel hybrid microsphere grafted silicon composite coating and preparation method thereof |
| CN106835824A (en) * | 2016-12-20 | 2017-06-13 | 宁波蓝星包装印务有限公司 | A kind of Packaging Box body paper material and preparation method thereof |
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| CN105368306A (en) * | 2015-10-28 | 2016-03-02 | 天长市润达金属防锈助剂有限公司 | Hydrophobic aluminum fluoride anti-corrosion Czochralski sol and preparation method thereof |
| 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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- 2016-06-12 CN CN201610420320.1A patent/CN105907225A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN105295064A (en) * | 2015-10-28 | 2016-02-03 | 天长市润达金属防锈助剂有限公司 | Oxidation resisting aluminum alloy corrosion preventing lifting sol and preparation method thereof |
| CN105368306A (en) * | 2015-10-28 | 2016-03-02 | 天长市润达金属防锈助剂有限公司 | Hydrophobic aluminum fluoride anti-corrosion Czochralski sol and preparation method thereof |
| 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 (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106700811A (en) * | 2016-12-20 | 2017-05-24 | 铜陵市经纬流体科技有限公司 | Aerogel hybrid microsphere grafted silicon composite coating and preparation method thereof |
| CN106835824A (en) * | 2016-12-20 | 2017-06-13 | 宁波蓝星包装印务有限公司 | A kind of Packaging Box body paper material and preparation method thereof |
| CN106835824B (en) * | 2016-12-20 | 2018-11-13 | 宁波市新兆印业有限公司 | A kind of Packaging Box body paper material and preparation method thereof |
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Application publication date: 20160831 |