CN105062355B - Nano-composite water durably anticorrosion paint preparation method for ship - Google Patents
Nano-composite water durably anticorrosion paint preparation method for ship Download PDFInfo
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- CN105062355B CN105062355B CN201510426564.6A CN201510426564A CN105062355B CN 105062355 B CN105062355 B CN 105062355B CN 201510426564 A CN201510426564 A CN 201510426564A CN 105062355 B CN105062355 B CN 105062355B
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 22
- 239000003973 paint Substances 0.000 title claims abstract description 13
- 239000002114 nanocomposite Substances 0.000 title claims abstract description 11
- 238000002360 preparation method Methods 0.000 title claims abstract description 9
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 22
- 229920002554 vinyl polymer Polymers 0.000 claims abstract description 17
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims abstract description 14
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000005543 nano-size silicon particle Substances 0.000 claims abstract description 12
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims abstract description 11
- 239000002245 particle Substances 0.000 claims abstract description 9
- 230000001476 alcoholic effect Effects 0.000 claims abstract description 8
- 235000012239 silicon dioxide Nutrition 0.000 claims abstract description 8
- 229910021529 ammonia Inorganic materials 0.000 claims abstract description 7
- 229920000642 polymer Polymers 0.000 claims abstract description 7
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 claims abstract description 7
- 235000019394 potassium persulphate Nutrition 0.000 claims abstract description 7
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 7
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 5
- 239000010703 silicon Substances 0.000 claims abstract description 5
- LFQCEHFDDXELDD-UHFFFAOYSA-N tetramethyl orthosilicate Chemical compound CO[Si](OC)(OC)OC LFQCEHFDDXELDD-UHFFFAOYSA-N 0.000 claims abstract description 5
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims abstract description 4
- FPCJKVGGYOAWIZ-UHFFFAOYSA-N butan-1-ol;titanium Chemical compound [Ti].CCCCO.CCCCO.CCCCO.CCCCO FPCJKVGGYOAWIZ-UHFFFAOYSA-N 0.000 claims abstract description 4
- 239000003999 initiator Substances 0.000 claims abstract description 4
- 229910010413 TiO 2 Inorganic materials 0.000 claims description 13
- 238000003756 stirring Methods 0.000 claims description 12
- -1 vinyl modified silicon dioxide Chemical class 0.000 claims description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 9
- 239000005977 Ethylene Substances 0.000 claims description 9
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 9
- 238000002156 mixing Methods 0.000 claims description 9
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 7
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 7
- 238000001704 evaporation Methods 0.000 claims description 6
- 230000008020 evaporation Effects 0.000 claims description 6
- 239000002904 solvent Substances 0.000 claims description 6
- 238000006243 chemical reaction Methods 0.000 claims description 5
- 238000000034 method Methods 0.000 claims description 5
- 239000008367 deionised water Substances 0.000 claims description 4
- 229910021641 deionized water Inorganic materials 0.000 claims description 4
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 3
- 239000002253 acid Substances 0.000 claims description 3
- 230000032683 aging Effects 0.000 claims description 3
- 239000007795 chemical reaction product Substances 0.000 claims description 3
- 239000012046 mixed solvent Substances 0.000 claims description 3
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 claims description 3
- 229910000077 silane Inorganic materials 0.000 claims description 2
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims 1
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 claims 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims 1
- 238000000576 coating method Methods 0.000 abstract description 24
- 239000011248 coating agent Substances 0.000 abstract description 23
- 238000005260 corrosion Methods 0.000 abstract description 9
- 230000007797 corrosion Effects 0.000 abstract description 8
- 238000005516 engineering process Methods 0.000 abstract description 4
- FWDBOZPQNFPOLF-UHFFFAOYSA-N ethenyl(triethoxy)silane Chemical compound CCO[Si](OCC)(OCC)C=C FWDBOZPQNFPOLF-UHFFFAOYSA-N 0.000 abstract description 3
- 238000006664 bond formation reaction Methods 0.000 abstract description 2
- 230000002401 inhibitory effect Effects 0.000 abstract description 2
- 238000006068 polycondensation reaction Methods 0.000 abstract description 2
- 230000005855 radiation Effects 0.000 abstract description 2
- 238000012986 modification Methods 0.000 abstract 1
- 230000004048 modification Effects 0.000 abstract 1
- 229910017604 nitric acid Inorganic materials 0.000 abstract 1
- 239000000758 substrate Substances 0.000 abstract 1
- 238000012360 testing method Methods 0.000 description 8
- 239000000463 material Substances 0.000 description 4
- 229910003978 SiClx Inorganic materials 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- CWAFVXWRGIEBPL-UHFFFAOYSA-N ethoxysilane Chemical compound CCO[SiH3] CWAFVXWRGIEBPL-UHFFFAOYSA-N 0.000 description 2
- 230000007935 neutral effect Effects 0.000 description 2
- 238000010422 painting Methods 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- 239000007921 spray Substances 0.000 description 2
- QQQSFSZALRVCSZ-UHFFFAOYSA-N triethoxysilane Chemical compound CCO[SiH](OCC)OCC QQQSFSZALRVCSZ-UHFFFAOYSA-N 0.000 description 2
- 239000003643 water by type Substances 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 1
- 239000002250 absorbent Substances 0.000 description 1
- 230000002745 absorbent Effects 0.000 description 1
- LFTIKJJFQYARGL-UHFFFAOYSA-L acetic acid;dichlorocopper Chemical compound Cl[Cu]Cl.CC(O)=O LFTIKJJFQYARGL-UHFFFAOYSA-L 0.000 description 1
- 230000002421 anti-septic effect Effects 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 230000001066 destructive effect Effects 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000003670 easy-to-clean Effects 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 1
- 230000003137 locomotive effect Effects 0.000 description 1
- 230000005923 long-lasting effect Effects 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000011858 nanopowder Substances 0.000 description 1
- 208000014451 palmoplantar keratoderma and congenital alopecia 2 Diseases 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 239000005871 repellent Substances 0.000 description 1
- 238000003980 solgel method Methods 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 230000008961 swelling Effects 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
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- Paints Or Removers (AREA)
Abstract
The present invention relates to corrosion-inhibiting coating technology of preparing, it is desirable to provide a kind of nano-composite water durably anticorrosion paint preparation method for ship.Including：Corpuscular type nano silicon dioxide sol is made to obtain in the saturation alcoholic solution of methyl silicate and ammonia, is further handled with nitric acid and butyl titanate, then carries out surface modification with VTES；Blended therewith after separately concentrating and nano combined performed polymer is made, added potassium peroxydisulfate as initiator, obtain product.The decay resistance of coating greatly improved in polycondensation and the high film forming matter of silica silicon bonding formation durability of the present invention by vinyl, nano-silicon dioxide modified dose of little particle.On the other hand, nano silicon can absorb ultraviolet radiation with submicron order rutile titanium dioxide, durability of coating is significantly strengthened.Coating only needs tens microns in ship substrate surface can obtain good decay resistance.
Description
Technical field
The present invention relates to corrosion-inhibiting coating technology of preparing, more particularly to for shell anti-corrosion, inorganic coating preparation side easy to clean
Method.
Background technology
Ship requires very high with anticorrosive paint especially shell anticorrosive paint to the decay resistance of coating, universal at present
The anticorrosive paint used is mainly organic water borne coating, including water-and acrylate, aqueous polyurethane, aqueous epoxy resins etc.,
Automobile making, external wall have been widely used in it, the field, the antiseptic effect played such as railway locomotive, traffic bridge.But it is organic
Class water-repellent preservation applies layer absorbent by force, can produce Swelling, causes coating cracking, therefore exist in ocean engineering application aspect and apply
Work thickness big (hundreds of microns), the problems such as service life is short.
On the other hand, hull easily pollutes in ocean, in destructive air throughout the year, and coating is by ultraviolet and wind and snow misty rain etc.
Harsh weather influence is notable, and the maintenance cost of hull paint film is very high.
In view of the above-mentioned problems, the present invention is using nano silicon and rutile type nano titanic oxide as nanometer phase, with many
Component silane copolymer is film forming matter, and excellent by the compound weather resistance for preparing of nanopowders by sol-gel method, anti-corrosive properties are high, with length
Imitate corrosion-resistant nano composite dope.
The content of the invention
The technical problem to be solved in the present invention is to overcome that of the prior art not enough there is provided a kind of nanometer for ship
Composite water soluble durably anticorrosion paint preparation method.
The invention provides a kind of nano-composite water durably anticorrosion paint preparation method for ship, including following step
Suddenly：
(1) under 500r/min stirring condition, by the saturated alcohols for the ammonia that 2 moles are added in 1 mole of methyl silicate
Solution, then adds water, and make the mol ratio of water and element silicon be 6~10: 1；Reacted at 60 DEG C after 8h, be aged 24h, added
10 moles of deionized waters stir, then rotated removed by evaporation mixed solvent 50% mass, obtain corpuscular type nano-silica
SiClx colloidal sol；
(2) under 500r/min stir speed (S.S.) and 55 DEG C of reaction temperatures, 4 molar nitric acids are added into 1 mole of deionized water
In be well mixed, then add 0.05 mole of butyl titanate, reaction 4 hours after, at room temperature it is closed ageing 6~10 hours, obtain
Rutile type nano titanic oxide sol；
(3) under 300r/min mixing speed, 1 molar ethylene base three is added into the silicon dioxide gel of step (1)
Ethoxysilane, 8h is reacted at 40~45 DEG C, obtains vinyl modified silicon dioxide gel；
(4) under 300r/min mixing speed, 0.05 molar ethylene base is added into the TiO 2 sol of step (2)
Triethoxysilane, 8h is reacted at 40 DEG C, obtains vinyl modified TiO 2 sol, at room temperature open evaporation of solvent
60% mass, the vinyl modified TiO 2 sol concentrated；
(5) under 300r/min stirring condition, vinyl modified silicon dioxide gel and step prepared by step (3)
(4) after the vinyl modified TiO 2 sol mixing of the concentration prepared, nitre acid for adjusting pH value is added into mixed sols, makes it
PH value is maintained at 1~3；It is stirred for after 0.5h, above-mentioned mixed sols is added dropwise in 3~5 molar ethylene ethyl triethoxy silicane alkane
In, reacted at 30 DEG C after 6h, nano combined performed polymer is made；
(6) potassium peroxydisulfate is added into the nano combined performed polymer of step (5) reaction product as initiator, potassium peroxydisulfate is accounted for
The 0.4~0.6% of VTES quality；4h is incubated at 70 DEG C, the painting of nano-composite water long-effective corrosion is obtained
Material.
In the present invention, in the saturation alcoholic solution of step (1) described ammonia, used alcoholic solvent is methanol, ethanol, isopropyl
Alcohol one of which or wherein several combinations.
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 invention has the advantages that：
The present invention is using homemade surface-modified high concentration little particle nano silicon and the rutile of sub-micron
Type TiO 2 sol coordinates as nanometer strengthener, the polycondensation and silica silicon bonding formation durability by vinyl it is high into
The decay resistance of coating greatly improved in film thing, nano-silicon dioxide modified dose of little particle.On the other hand, nano silicon
Ultraviolet radiation is can absorb with submicron order rutile titanium dioxide, durability of coating is significantly strengthened.Coating is in ship base
Material surface, which only needs tens microns, can obtain good decay resistance.
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 ship comprises the following steps：
(1) under 500r/min stirring condition, by the saturated alcohols for the ammonia that 2 moles are added in 1 mole of methyl silicate
Solution, then adds water, and make the mol ratio of water and element silicon be 6~10: 1；Reacted at 60 DEG C after 8h, be aged 24h, added
10 moles of deionized waters stir, then rotated removed by evaporation mixed solvent 50% mass, obtain corpuscular type nano-silica
SiClx colloidal sol；
(2) under 500r/min stir speed (S.S.) and 55 DEG C of reaction temperatures, 4 molar nitric acids are added into 1 mole of deionized water
In be well mixed, then add 0.05 mole of butyl titanate, reaction 4 hours after, at room temperature it is closed ageing 6~10 hours, obtain
Rutile type nano titanic oxide sol；
(3) under 300r/min mixing speed, 1 molar ethylene base three is added into the silicon dioxide gel of step (1)
Ethoxysilane, 8h is reacted at 40~45 DEG C, obtains vinyl modified silicon dioxide gel；
(4) under 300r/min mixing speed, 0.05 molar ethylene base is added into the TiO 2 sol of step (2)
Triethoxysilane, 8h is reacted at 40 DEG C, obtains vinyl modified TiO 2 sol, at room temperature open evaporation of solvent
60% mass, the vinyl modified TiO 2 sol concentrated；
(5) under 300r/min stirring condition, vinyl modified silicon dioxide gel and step prepared by step (3)
(4) after the vinyl modified TiO 2 sol mixing of the concentration prepared, nitre acid for adjusting pH value is added into mixed sols, makes it
PH value is maintained at 1~3；It is stirred for after 0.5h, above-mentioned mixed sols is added dropwise in 3~5 molar ethylene ethyl triethoxy silicane alkane
In, reacted at 30 DEG C after 6h, nano combined performed polymer is made；
(6) potassium peroxydisulfate is added into the nano combined performed polymer of step (5) reaction product as initiator, potassium peroxydisulfate is accounted for
The 0.4~0.6% of VTES quality；4h is incubated at 70 DEG C, the painting of nano-composite water long-effective corrosion is obtained
Material.
In the saturation alcoholic solution of step (1) described ammonia, used alcoholic solvent is methanol, ethanol, isopropanol wherein one
Plant or wherein several combinations.
In the present invention, the application method of obtained nano-composite water durably anticorrosion paint：
Coating by spraying method metal surface coat, at room temperature after surface drying 30min, after solidifying through 24h formed 40~
50 microns of thick long lasting anticorrosion coatings.
Coating uses following standard testing various aspects of performance：1) coating pencil hardness uses U.S. material association ASTM3363
Standard testing；2) durability of coating experiment is using standard GB/T-T1865-1997 tests；3) coating neutral salt spray test is used
Acetic acid copper chloride salt fog accelerated test (CASS testing standards) is tested.
Test data in various embodiments of the present invention see the table below：
As can be seen from the table, coating corrosion resistant prepared by the sample coating (sequence number 2-10) of nano silicon dioxide sol is added
Corrosion can be very high with weatherability, respectively 30 days and more than 70 days, and the example of non-plus nano silicon dioxide gel is applied
Expect that the coating corrosion resistance prepared can be relatively low with weatherability, respectively 10 days and 30 days.Other performances of coating are such as：Pencil is hard
Significant change does not occur for degree, decay resistance (neutral salt spray test) etc..It can be seen that, the addition of nano titanium oxide is not influenceing to apply
The self-cleaning performance of coating is largely improved on the premise of other performances of layer.
Finally, in addition it is also necessary to it is noted that listed above is only specific embodiment of the invention.Obviously, the present invention not
It is limited to above embodiment, there can also be many deformations.One of ordinary skill in the art can be straight from present disclosure
Export or all deformations associated are connect, protection scope of the present invention is considered as.
Claims (4)
1. a kind of nano-composite water durably anticorrosion paint preparation method for ship, it is characterised in that comprise the following steps：
(1) under 500r/min stirring condition, by the saturation alcoholic solution for the ammonia that 2 moles are added in 1 mole of methyl silicate,
Then water is added, and makes the mol ratio of water and element silicon be 6~10: 1；Reacted at 60 DEG C after 8h, be aged 24h, added 10 and rub
Your deionized water stirs, then rotated removed by evaporation mixed solvent 50% mass, obtain corpuscular type nano silicon
Colloidal sol；
(2) under 500r/min stir speed (S.S.) and 55 DEG C of reaction temperatures, 4 molar nitric acids is added in 1 mole of deionized water and mixed
Close uniform, then add 0.05 mole of butyl titanate, after reacting 4 hours, closed ageing 6~10 hours, obtain golden red at room temperature
Stone-type nano titanic oxide sol；
(3) under 300r/min mixing speed, the ethoxy of 1 molar ethylene base three is added into the silicon dioxide gel of step (1)
Base silane, 8h is reacted at 40~45 DEG C, obtains vinyl modified silicon dioxide gel；
(4) under 300r/min mixing speed, the second of 0.05 molar ethylene base three is added into the TiO 2 sol of step (2)
TMOS, 8h is reacted at 40 DEG C, obtains vinyl modified TiO 2 sol, at room temperature open evaporation of solvent
60% mass, the vinyl modified TiO 2 sol concentrated；
(5) under 300r/min stirring condition, vinyl modified silicon dioxide gel prepared by step (3) and step (4)
After the vinyl modified TiO 2 sol mixing of the concentration of preparation, nitre acid for adjusting pH value is added into mixed sols, makes its pH
Value is maintained at 1~3；It is stirred for after 0.5h, 3~5 molar ethylene ethyl triethoxy silicane alkane is added dropwise in above-mentioned mixed sols,
Reacted at 30 DEG C after 6h, nano combined performed polymer is made；
(6) potassium peroxydisulfate is added into the nano combined performed polymer of step (5) reaction product as initiator, potassium peroxydisulfate accounts for ethene
The 0.4~0.6% of ethyl triethoxy silicane alkane quality；4h is incubated at 70 DEG C, nano-composite water durably anticorrosion paint is obtained.
2. according to the method described in claim 1, it is characterised in that in the saturation alcoholic solution of step (1) described ammonia, used
Alcoholic solvent be methanol, ethanol, isopropanol one of which or wherein several combinations.
3. according to the method described in claim 1, it is characterised in that the nano silicon dioxide sol particle in step (1) is averaged
Particle diameter is 3~5nm.
4. according to the method described in claim 1, it is characterised in that the nano titanic oxide sol particle in step (2) is averaged
Particle diameter is 150~200nm.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510426564.6A CN105062355B (en) | 2015-07-20 | 2015-07-20 | Nano-composite water durably anticorrosion paint preparation method for ship |
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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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| CN105062355B true CN105062355B (en) | 2017-08-25 |
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| CN114657546B (en) * | 2022-04-07 | 2022-11-15 | 武汉铁路职业技术学院 | Anti-corrosion treatment process for railway track embedded part |
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