CN106085089A - A kind of aeroge metallic copper corrosion-inhibiting coating and preparation method thereof - Google Patents
A kind of aeroge metallic copper corrosion-inhibiting coating and preparation method thereof Download PDFInfo
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- 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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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
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- C08G77/20—Polysiloxanes containing silicon bound to unsaturated aliphatic groups
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- 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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- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
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- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
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- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
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- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
- C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend
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Abstract
The invention discloses a kind of aeroge metallic copper corrosion-inhibiting coating, this coating is made up of the raw material of following weight parts: sodium monofluorophosphate 12, Colophonium 0.7 1, aerosil 24, methyl benzotriazazole 12, Hydroxypropyl methacrylate 0.1 0.2, alkylpolyoxyethylene 0.5 1, vinyltrimethoxy silane 10 14, the citric acid solution 200 300 of 1.8 2g/l, silane coupler KBM510313 17, tetraethyl orthosilicate 100 110, hexafluorobutyl acrylate 30 37, azodiisobutyronitrile 0.1 0.14, the ammonia 57 of 20 25%, ferroso-ferric oxide 45, alkenyl succinic acid 12, polyoxyethylene sorbitan monoleate 0.1 0.3.The present invention can form the hybrid coating surface of various different-shape, and the coating surface of different structure combines the vinyl group of exposed low-surface-energy, jointly imparts coating and has superhydrophobic characteristic.
Description
Technical field
The present invention relates to technical field of metal anti-corrosion, particularly relate to a kind of aeroge metallic copper corrosion-inhibiting coating and preparation side thereof
Method.
Background technology
In recent years, along with the enhancing of people's environmental consciousness, traditional protection by metallic coating or surface treatment method face sternly
High challenge, though as 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 of metal surface processes skill
Art, sediment and phosphate that phosphating process produces easily cause the oxygen enrichment of water quality, the dirt to water quality of nitrite, heavy metal ion
Dye etc. also needs to seek new surface treatment method.In recent years, new eco-friendly surface-coating technology arises at the historic moment, as imitated
The bionical selfreparing corrosion-inhibiting coating of organism self-repair function principle, self-assembled monolayer technology, super-hydrophobic film technology, it is worth
One is mentioned that, owing to super-hydrophobic film technology is lossless defeated at anticorrosion inhibition, self-cleaning surface, frost resistance, Drag Reduction and microfluid
Send, biotechnology field shows great using value and causes the extensive concern of people, and the research in this field is non-
The most active.Super-hydrophobic film technology be according to water droplet can on super hydrophobic surface free rolling phenomenon-" lotus leaf effect " and carry
A kind of metal surface treating method gone out.Surface is jointly imparted super thin at the micro nano structure of lotus leaf surface and top layer matter thereof
Aqueous energy.Super hydrophobic surface micro nano structure can improve static contact angle, makes drop be difficult to penetrate into micro-nano coarse structure, makes
Become the physical isolation of metal and Korrosionsmedium, reach etch-proof purpose.Treatment of Metal Surface based on super-hydrophobic film technology
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, become one the most promising protecting metallic surface method；
Affecting the infiltrating key factor of the surface of solids is surface free energy, when surface free energy reduces, and 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, because of
This, only can not obtain super hydrophobic surface by fall low-surface-energy.
Existing research shows, builds super hydrophobic surface mainly by two approach, and the first is at the substrate surface of raw sugar
Modify low-surface energy substance;It two is to build at hydrophobic surface to have the micro nano structure of certain raw sugar degree, according to these two ways
Footpath, scientists has developed the method for a lot of structure super hydrophobic surface, has 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 the most promising metal watch
One of face means of defence；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 aeroge metallic copper corrosion-inhibiting coating and
Preparation method.
The present invention is achieved by the following technical solutions:
A kind of aeroge metallic copper corrosion-inhibiting coating, this coating is made up of the raw material of following weight parts:
Sodium monofluorophosphate 1-2, Colophonium 0.7-1, aerosil 2-4, methyl benzotriazazole 1-2, hydroxyethyl methacrylate
Propyl ester 0.1-0.2, alkylpolyoxyethylene 0.5-1, the citric acid of vinyltrimethoxy silane 10-14,1.8-2g/l
Solution 200-300, silane coupler KBM510313-17, tetraethyl orthosilicate 100-110, hexafluorobutyl acrylate 30-37, azo
The ammonia 5-7 of bis-isobutyronitrile 0.1-0.14,20-25%, ferroso-ferric oxide 4-5, alkenyl succinic acid 1-2, polyoxyethylene sorbitan monoleate 0.1-
0.3。
The preparation method of the aeroge 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, will
Filter cake absolute ethanol washing 2-3 time, is vacuum dried 10-20 minute at 76-80 DEG C, obtains sour modification ferroso-ferric oxide；
(2) above-mentioned methyl benzotriazazole is joined in the dehydrated alcohol of its weight 6-9 times, rise high-temperature and be 50-60 DEG C, add
Entering alkylpolyoxyethylene, stirring, to room temperature, obtains alcohol emulsion；
(3) 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, adding above-mentioned silane coupler KBM5103, tetraethyl orthosilicate, 700-1000 rev/min of stirring is reacted 6-7 hour,
Add above-mentioned alcohol emulsion, stir, sucking filtration, by filter cake absolute ethanol washing 2-3 time, it is vacuum dried at 100-110 DEG C
20-25 hour, obtain ethenyl blocking composite；
(4) above-mentioned ethenyl blocking composite is joined in the dimethylformamide of its weight 100-105 times, ultrasonic 40-
50 minutes, it is passed through nitrogen, adds aforesaid propylene acid hexafluoro butyl ester, azodiisobutyronitrile, react 5-7 hour at 70-80 DEG C, cold
But 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；
(5) above-mentioned aerosil is joined in its weight 6-8 times, 30-35% ethanol, add above-mentioned poly-Pyrusussuriensis
Ester 80, insulated and stirred 4-5 minute at 60-70 DEG C, add above-mentioned fluorination composite, 100-200 rev/min of stirring 10-17 divides
Clock, obtains gel alcohol dispersion liquid；
(6) above-mentioned Colophonium is joined in the ethanol solution of its weight 35-40 times, 95-97%, rise high-temperature and be 70-76 DEG C, protect
Temperature stirring 10-13 minute, adds above-mentioned gel alcohol dispersion liquid, ultrasonic disperse 10-20 minute, adds and remains each raw material, and stirring is all
Even, 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, initially with citric acid modification magnetic Fe 304 nanoparticle, can make its conduct
Aqueous favoring is the most molten with silane coupler KBM5103, and then the hydrolysis by silane coupler KBM5103 and tetraethyl orthosilicate is anti-
Should, introduce the siloxanes of ethenyl blocking on ferroso-ferric oxide surface, provide vinyl active group for graft polymerization reaction.Third
Olefin(e) acid hexafluoro butyl ester passes through glycerol polymerization, at compound particle table with the ferroso-ferric oxide/siloxanes compound particle of ethenyl blocking
Face forms fluoropolymer, is then joined in silanol liquid by fluoropolymer compound particle, reduces the surface energy of coating,
Improve the hydrophobic performance of coating；This silanol liquid with vinyltrimethoxy silane as presoma, ammonia as catalyst, vinyl
Trimethoxy silane first occurs hydrolysis to generate silanol, the most in the basic conditions dehydrogenation, and other silicon atomic core are started parent
Nuclear attack, occurs condensation reaction to form Si-0-Si key, and along with dehydration or dealcoholysis, progressively assembles nucleation, life at copper-based surfaces
Long, ultimately form the hybrid coating surface of various different-shape, the coating surface of different structure combines exposed low surface
The vinyl group of energy, jointly imparts coating and has superhydrophobic characteristic.Present invention adds aeroge, effectively raise filler
Particle dispersibility in the polymer, improves stability and the surface strength of finished product coating.
Detailed description of the invention
A kind of aeroge metallic copper corrosion-inhibiting coating, this coating is made up of the raw material of following weight parts:
Sodium monofluorophosphate 1, Colophonium 0.7, aerosil 2, methyl benzotriazazole 1, Hydroxypropyl methacrylate 0.1,
Alkylpolyoxyethylene 0.5, vinyltrimethoxy silane 10, the citric acid solution 200 of 1.8g/l, silane coupler
KBM510313, tetraethyl orthosilicate 100, hexafluorobutyl acrylate 30, ammonia 5, four oxidation three of azodiisobutyronitrile 0.1,20%
Ferrum 4, alkenyl succinic acid 1, polyoxyethylene sorbitan monoleate 0.1.
The preparation method of the aeroge metallic copper corrosion-inhibiting coating described in a kind of claim 1, comprises the following steps:
(1) being joined by above-mentioned ferroso-ferric oxide in the citric acid solution of 1.8g/l, ultrasonic disperse 1.7 hours, sucking filtration, by filter cake
With absolute ethanol washing 2 times, it is vacuum dried 10 minutes at 76 DEG C, obtains sour modification ferroso-ferric oxide；
(2) being joined by above-mentioned methyl benzotriazazole in the dehydrated alcohol of its weight 6 times, rising high-temperature is 50 DEG C, adds ten
Dialkyl group polyoxyethylene ether, stirring, to room temperature, obtains alcohol emulsion；
(3) ferroso-ferric oxide is modified in above-mentioned acid and join in its weight 370 times, the ethanol solution of 30%, ultrasonic 20 minutes,
Adding above-mentioned silane coupler KBM5103, tetraethyl orthosilicate, 700 revs/min of stirrings are reacted 6 hours, add above-mentioned alcohol emulsion, stir
Mix uniformly, sucking filtration, by filter cake absolute ethanol washing 2 times, it is vacuum dried 20 hours at 100 DEG C, obtains ethenyl blocking and be combined
Material；
(4) 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, be cooled to room temperature, take out
Filter, washes filter cake dimethylformamide 3 times, is vacuum dried 10 hours, obtains fluorination composite at 80 DEG C；
(5) above-mentioned aerosil is joined in its weight 6 times, the ethanol of 30%, adds above-mentioned polyoxyethylene sorbitan monoleate,
Insulated and stirred 4 minutes at 60 DEG C, add above-mentioned fluorination composite, and 100 revs/min are stirred 10 minutes, obtain gel alcohol dispersion liquid；
(6) above-mentioned Colophonium is joined its weight 35 times, 95% ethanol solution in, rise high-temperature be 70 DEG C, insulated and stirred 10 points
Clock, adds above-mentioned gel alcohol dispersion liquid, ultrasonic disperse 10 minutes, add and remain each raw material, stir, and puts into and cleans up
Copper sheet, soaks 20 hours, takes out, and is dried, obtains described coating at 60 DEG C.
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；This
Bright coating 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, stands 30 minutes, then measure its contact angle, pH be 2-12 this
In the range of individual, contact angle is both greater than 150 °, illustrate strong acid, highly basic to superhydrophobic surface structure and chemical composition thereof almost without shadow
Ringing, the coating that this composite particles is formed has good acid-proof alkaline.
Claims (2)
1. an aeroge metallic copper corrosion-inhibiting coating, it is characterised in that this coating is made up of the raw material of following weight parts:
Sodium monofluorophosphate 1-2, Colophonium 0.7-1, aerosil 2-4, methyl benzotriazazole 1-2, hydroxyethyl methacrylate
Propyl ester 0.1-0.2, alkylpolyoxyethylene 0.5-1, the citric acid of vinyltrimethoxy silane 10-14,1.8-2g/l
Solution 200-300, silane coupler KBM510313-17, tetraethyl orthosilicate 100-110, hexafluorobutyl acrylate 30-37, azo
The ammonia 5-7 of bis-isobutyronitrile 0.1-0.14,20-25%, ferroso-ferric oxide 4-5, alkenyl succinic acid 1-2, polyoxyethylene sorbitan monoleate 0.1-
0.3。
2. the preparation method of the aeroge metallic copper corrosion-inhibiting coating described in a claim 1, it is characterised in that include following step
Rapid:
(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, will
Filter cake absolute ethanol washing 2-3 time, is vacuum dried 10-20 minute at 76-80 DEG C, obtains sour modification ferroso-ferric oxide；
(2) above-mentioned methyl benzotriazazole is joined in the dehydrated alcohol of its weight 6-9 times, rise high-temperature and be 50-60 DEG C, add
Entering alkylpolyoxyethylene, stirring, to room temperature, obtains alcohol emulsion；
(3) 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, adding above-mentioned silane coupler KBM5103, tetraethyl orthosilicate, 700-1000 rev/min of stirring is reacted 6-7 hour,
Add above-mentioned alcohol emulsion, stir, sucking filtration, by filter cake absolute ethanol washing 2-3 time, it is vacuum dried at 100-110 DEG C
20-25 hour, obtain ethenyl blocking composite；
(4) above-mentioned ethenyl blocking composite is joined in the dimethylformamide of its weight 100-105 times, ultrasonic 40-
50 minutes, it is passed through nitrogen, adds aforesaid propylene acid hexafluoro butyl ester, azodiisobutyronitrile, react 5-7 hour at 70-80 DEG C, cold
But 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；
(5) above-mentioned aerosil is joined in its weight 6-8 times, 30-35% ethanol, add above-mentioned poly-Pyrusussuriensis
Ester 80, insulated and stirred 4-5 minute at 60-70 DEG C, add above-mentioned fluorination composite, 100-200 rev/min of stirring 10-17 divides
Clock, obtains gel alcohol dispersion liquid；
(6) above-mentioned Colophonium is joined in the ethanol solution of its weight 35-40 times, 95-97%, rise high-temperature and be 70-76 DEG C, protect
Temperature stirring 10-13 minute, adds above-mentioned gel alcohol dispersion liquid, ultrasonic disperse 10-20 minute, adds and remains each raw material, and stirring is all
Even, 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 (5)
| 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 |
| CN106810991A (en) * | 2016-12-20 | 2017-06-09 | 铜陵市经纬流体科技有限公司 | A kind of anti-oxidant hybrid microspheres grafting silicon composite coating and preparation method thereof |
| CN106810990A (en) * | 2016-12-20 | 2017-06-09 | 铜陵市经纬流体科技有限公司 | A kind of polymer hybridisation microsphere grafting silicon composite coating and preparation method thereof |
| CN109024075A (en) * | 2018-07-12 | 2018-12-18 | 江苏金大包装材料科技有限公司 | A kind of antibacterial release paper and preparation method thereof |
| CN112542277A (en) * | 2020-11-18 | 2021-03-23 | 郑艳亭 | Preparation process of high-flame-retardant cable of power line |
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| 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 |
-
2016
- 2016-06-13 CN CN201610420427.6A patent/CN106085089A/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 (5)
| 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 |
| CN106810991A (en) * | 2016-12-20 | 2017-06-09 | 铜陵市经纬流体科技有限公司 | A kind of anti-oxidant hybrid microspheres grafting silicon composite coating and preparation method thereof |
| CN106810990A (en) * | 2016-12-20 | 2017-06-09 | 铜陵市经纬流体科技有限公司 | A kind of polymer hybridisation microsphere grafting silicon composite coating and preparation method thereof |
| CN109024075A (en) * | 2018-07-12 | 2018-12-18 | 江苏金大包装材料科技有限公司 | A kind of antibacterial release paper and preparation method thereof |
| CN112542277A (en) * | 2020-11-18 | 2021-03-23 | 郑艳亭 | Preparation process of high-flame-retardant cable of power line |
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Application publication date: 20161109 |
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| RJ01 | Rejection of invention patent application after publication |