CN105062355A - Preparation method for nano compound water-based controlled release anticorrosive paint for ships - Google Patents
Preparation method for nano compound water-based controlled release anticorrosive paint for ships Download PDFInfo
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- CN105062355A CN105062355A CN201510426564.6A CN201510426564A CN105062355A CN 105062355 A CN105062355 A CN 105062355A CN 201510426564 A CN201510426564 A CN 201510426564A CN 105062355 A CN105062355 A CN 105062355A
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Abstract
The invention relates to the preparation technique of anticorrosive coatings, and aims to provide a preparation method for nano compound water-based controlled release anticorrosive paint for ships. The preparation method comprises the following steps: preparing particle-type nano silicon dioxide sol from tetramethyl orthosilicate and a saturated alcohol solution of ammonia gas, conducting further treatment through nitric acid and butyl titanate, and conducting surface modification through vinyl triethoxy silane to obtain vinyl modified silicon dioxide sol; conducting concentration to obtain vinyl modified titanium dioxide sol, mixing vinyl modified silicon dioxide sol and concentrated vinyl modified titanium dioxide sol to obtain nano composite prepolymer, and adding potassium peroxodisulfate as an initiating agent to obtain the product. According to the preparation method, film forming matters with high durability are formed through polycondensation of vinyl and bonding of siloxanyl, and the corrosion resistance of a coating is greatly improved through a small particle nano silicon dioxide modifying agent. Moreover, nano silicon dioxide and submicron rutile titanium dioxide can absorb ultraviolet light radiation, so that the weatherability of the coating is greatly improved; excellent corrosion resistance can be obtained only by dozens of micrometers of the coating on the surface of a ship base material.
Description
Technical field
The present invention relates to corrosion protection coating technology of preparing, particularly inorganic coating preparation method anticorrosion for shell, easy to clean.
Background technology
Boats and ships protective system especially shell protective system requires very high to the corrosion resistance nature of coating, the protective system generally used at present is mainly organic water borne coating, comprise water-and acrylate, aqueous polyurethane, aqueous epoxy resins etc., automobile making, external wall are widely used in, the fields such as railway locomotive, traffic bridge, the preservative effect played.But it is strong that organic water-repellent preservation is coated with layer absorbent, can produce Swelling, cause coating cracking, therefore there is the problems such as construction thickness large (hundreds of micron), work-ing life is short in oceanographic engineering application aspect.
On the other hand, hull is in that ocean is easily polluted throughout the year, in destructive air, coating affects significantly by atrocious weather such as ultraviolet and wind and snow misty rains, and the maintenance cost of hull paint film is very high.
For the problems referred to above, the present invention for nanophase, with polycomponent silane copolymer for filmogen, prepares weather resistance by nanopowders by sol-gel method compound excellent with nano silicon and rutile type nano titanic oxide, preservative property are high, have the nano composite dope of long-effective corrosion.
Summary of the invention
The technical problem to be solved in the present invention is, overcomes deficiency of the prior art, provides a kind of nano-composite water durably anticorrosion paint preparation method for boats and ships.
The invention provides a kind of nano-composite water durably anticorrosion paint preparation method for boats and ships, comprise the steps:
(1) under the agitation condition of 500r/min, by adding the saturated alcohol solution of the ammonia of 2 moles in 1 mole of methyl silicate, then add water, and make the mol ratio of water and element silicon be 6 ~ 10: 1; React 8h at 60 DEG C after, ageing 24h, adds 10 moles of deionized water and stirring evenly, then removes 50% quality of mixed solvent through rotary evaporation, obtain corpuscular type nano silicon dioxide sol;
(2) under the stir speed (S.S.) and 55 DEG C of temperature of reaction of 500r/min, 4 molar nitric acids are added in 1 mole of deionized water and mix, then add 0.05 mole of butyl (tetra) titanate, react after 4 hours, under room temperature, airtight ageing 6 ~ 10 hours, obtains rutile type nano titanic oxide sol;
(3) under the stirring velocity of 300r/min, in the silicon dioxide gel of step (1), add 1 molar ethylene ethyl triethoxy silicane alkane, at 40 ~ 45 DEG C, react 8h, obtain vinyl modified silicon dioxide gel;
(4) under the stirring velocity of 300r/min, 0.05 molar ethylene ethyl triethoxy silicane alkane is added in the TiO 2 sol of step (2), 8h is reacted at 40 DEG C, obtain vinyl modified TiO 2 sol, at room temperature 60% quality of uncovered evaporation of solvent, obtains the vinyl modified TiO 2 sol concentrated;
(5) under the agitation condition of 300r/min, after concentrated vinyl modified TiO 2 sol prepared by vinyl modified silicon dioxide gel step (3) prepared and step (4) mixes, in mixed sols, add nitric acid adjust ph, make its pH value remain on 1 ~ 3; After stirring 0.5h again, 3 ~ 5 molar ethylene ethyl triethoxy silicane alkane are dropwise added in above-mentioned mixed sols, react 6h at 30 DEG C after, obtained nano combined performed polymer;
(6) in the nano combined performed polymer of step (5) reaction product, add Potassium Persulphate as initiator, Potassium Persulphate accounts for 0.4 ~ 0.6% of vinyltriethoxysilane quality; At 70 DEG C, be incubated 4h, obtain nano-composite water durably anticorrosion paint.
In the present invention, the combination that in the saturated alcohol solution of step (1) described ammonia, the alcoholic solvent used is methyl alcohol, ethanol, Virahol are wherein a kind of or wherein several.
In the present invention, the nano silicon dioxide sol mean particle size in step (1) is 3 ~ 5nm.
In the present invention, the nano titanic oxide sol mean particle size in step (2) is 150 ~ 200nm.
Compared with existing technology of preparing, the present invention has following beneficial effect:
The present invention adopts the homemade high density small-particle nano silicon through surface modification to coordinate as nanometer strengthener with the rutile titanium dioxide colloidal sol of submicron, form the high film forming matter of weather resistance by the polycondensation of vinyl and silica silicon bonding, nano-silicon dioxide modified dose of small-particle significantly improves the corrosion resistance nature of coating.On the other hand, nano silicon and submicron order rutile titanium dioxide Absorbable rod ultraviolet radiation, make durability of coating significantly strengthen.Coating only needs tens microns can obtain good corrosion resistance nature at boats and ships substrate surface.
Embodiment
Below by way of example, the present invention is further described.
In the present invention, the nano-composite water durably anticorrosion paint preparation method for boats and ships comprises the steps:
(1) under the agitation condition of 500r/min, by adding the saturated alcohol solution of the ammonia of 2 moles in 1 mole of methyl silicate, then add water, and make the mol ratio of water and element silicon be 6 ~ 10: 1; React 8h at 60 DEG C after, ageing 24h, adds 10 moles of deionized water and stirring evenly, then removes 50% quality of mixed solvent through rotary evaporation, obtain corpuscular type nano silicon dioxide sol;
(2) under the stir speed (S.S.) and 55 DEG C of temperature of reaction of 500r/min, 4 molar nitric acids are added in 1 mole of deionized water and mix, then add 0.05 mole of butyl (tetra) titanate, react after 4 hours, under room temperature, airtight ageing 6 ~ 10 hours, obtains rutile type nano titanic oxide sol;
(3) under the stirring velocity of 300r/min, in the silicon dioxide gel of step (1), add 1 molar ethylene ethyl triethoxy silicane alkane, at 40 ~ 45 DEG C, react 8h, obtain vinyl modified silicon dioxide gel;
(4) under the stirring velocity of 300r/min, 0.05 molar ethylene ethyl triethoxy silicane alkane is added in the TiO 2 sol of step (2), 8h is reacted at 40 DEG C, obtain vinyl modified TiO 2 sol, at room temperature 60% quality of uncovered evaporation of solvent, obtains the vinyl modified TiO 2 sol concentrated;
(5) under the agitation condition of 300r/min, after concentrated vinyl modified TiO 2 sol prepared by vinyl modified silicon dioxide gel step (3) prepared and step (4) mixes, in mixed sols, add nitric acid adjust ph, make its pH value remain on 1 ~ 3; After stirring 0.5h again, 3 ~ 5 molar ethylene ethyl triethoxy silicane alkane are dropwise added in above-mentioned mixed sols, react 6h at 30 DEG C after, obtained nano combined performed polymer;
(6) in the nano combined performed polymer of step (5) reaction product, add Potassium Persulphate as initiator, Potassium Persulphate accounts for 0.4 ~ 0.6% of vinyltriethoxysilane quality; At 70 DEG C, be incubated 4h, obtain nano-composite water durably anticorrosion paint.
In the saturated alcohol solution of step (1) described ammonia, the combination that the alcoholic solvent used is methyl alcohol, ethanol, Virahol are wherein a kind of or wherein several.
In the present invention, the using method of obtained nano-composite water durably anticorrosion paint:
Coating is applied in metallic surface by spraying method, under room temperature after surface drying 30min, forms the long lasting anticorrosion coating of 40 ~ 50 micron thickness after 24h solidification.
Coating adopts following standard testing various aspects of performance: 1) coating pencil hardness adopts U.S. material association ASTM3363 standard testing; 2) durability of coating test adopts standard GB/T-T1865-1997 test; 3) coating neutral salt spray test adopts acetic acid cupric chloride salt fog accelerated test (CASS testing standard) test.
Testing data in various embodiments of the present invention sees the following form:
As can be seen from the table, the coating corrosion resistance prepared of the sample coating (sequence number 2-10) adding nano silicon dioxide sol can and weathering resistance all very high, respectively more than 30 days and 70 days, and coating corrosion resistance prepared by the example coating of non-plus nano silicon dioxide gel can and weathering resistance lower, be respectively 10 days and 30 days.Other performances of coating as: there is not considerable change in pencil hardness, corrosion resistance nature (neutral salt spray test) etc.Visible, nano titanium oxide be added in the prerequisite not affecting other performances of coating under improve the self-cleaning performance of coating largely.
Finally, it is also to be noted that enumerate above be only specific embodiments of the invention son.Obviously, the invention is not restricted to above examples of implementation, many distortion can also be had.All distortion that those of ordinary skill in the art can directly derive from content disclosed by the invention or associate, all should think protection scope of the present invention.
Claims (4)
1., for a nano-composite water durably anticorrosion paint preparation method for boats and ships, it is characterized in that, comprise the steps:
(1) under the agitation condition of 500r/min, by adding the saturated alcohol solution of the ammonia of 2 moles in 1 mole of methyl silicate, then add water, and make the mol ratio of water and element silicon be 6 ~ 10: 1; React 8h at 60 DEG C after, ageing 24h, adds 10 moles of deionized water and stirring evenly, then removes 50% quality of mixed solvent through rotary evaporation, obtain corpuscular type nano silicon dioxide sol;
(2) under the stir speed (S.S.) and 55 DEG C of temperature of reaction of 500r/min, 4 molar nitric acids are added in 1 mole of deionized water and mix, then add 0.05 mole of butyl (tetra) titanate, react after 4 hours, under room temperature, airtight ageing 6 ~ 10 hours, obtains rutile type nano titanic oxide sol;
(3) under the stirring velocity of 300r/min, in the silicon dioxide gel of step (1), add 1 molar ethylene ethyl triethoxy silicane alkane, at 40 ~ 45 DEG C, react 8h, obtain vinyl modified silicon dioxide gel;
(4) under the stirring velocity of 300r/min, 0.05 molar ethylene ethyl triethoxy silicane alkane is added in the TiO 2 sol of step (2), 8h is reacted at 40 DEG C, obtain vinyl modified TiO 2 sol, at room temperature 60% quality of uncovered evaporation of solvent, obtains the vinyl modified TiO 2 sol concentrated;
(5) under the agitation condition of 300r/min, after concentrated vinyl modified TiO 2 sol prepared by vinyl modified silicon dioxide gel step (3) prepared and step (4) mixes, in mixed sols, add nitric acid adjust ph, make its pH value remain on 1 ~ 3; After stirring 0.5h again, 3 ~ 5 molar ethylene ethyl triethoxy silicane alkane are dropwise added in above-mentioned mixed sols, react 6h at 30 DEG C after, obtained nano combined performed polymer;
(6) in the nano combined performed polymer of step (5) reaction product, add Potassium Persulphate as initiator, Potassium Persulphate accounts for 0.4 ~ 0.6% of vinyltriethoxysilane quality; At 70 DEG C, be incubated 4h, obtain nano-composite water durably anticorrosion paint.
2. method according to claim 1, is characterized in that, the combination that in the saturated alcohol solution of step (1) described ammonia, the alcoholic solvent used is methyl alcohol, ethanol, Virahol are wherein a kind of or wherein several.
3. method according to claim 1, is characterized in that, the nano silicon dioxide sol mean particle size in step (1) is 3 ~ 5nm.
4. method according to claim 1, is characterized in that, the nano titanic oxide sol mean particle size in step (2) is 150 ~ 200nm.
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| CN201510426564.6A CN105062355B (en) | 2015-07-20 | 2015-07-20 | Nano-composite water durably anticorrosion paint preparation method for ship |
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| CN105062355A true CN105062355A (en) | 2015-11-18 |
| CN105062355B CN105062355B (en) | 2017-08-25 |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105860833A (en) * | 2016-06-04 | 2016-08-17 | 金华格灵功能涂层材料研究所有限公司 | Preparation method of alcohol-group aluminum alloy hub coating |
| CN114657546A (en) * | 2022-04-07 | 2022-06-24 | 武汉铁路职业技术学院 | Anti-corrosion treatment process for railway track embedded part |
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- 2015-07-20 CN CN201510426564.6A patent/CN105062355B/en not_active Expired - Fee Related
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105860833A (en) * | 2016-06-04 | 2016-08-17 | 金华格灵功能涂层材料研究所有限公司 | Preparation method of alcohol-group aluminum alloy hub coating |
| CN114657546A (en) * | 2022-04-07 | 2022-06-24 | 武汉铁路职业技术学院 | Anti-corrosion treatment process for railway track embedded part |
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