CN106479354B - A kind of antifouling anticorrosive nano polysiloxane coating materials of primer-topcoat in one and preparation method thereof - Google Patents
A kind of antifouling anticorrosive nano polysiloxane coating materials of primer-topcoat in one and preparation method thereof Download PDFInfo
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- 238000000576 coating method Methods 0.000 title claims abstract description 66
- 239000011248 coating agent Substances 0.000 title claims abstract description 65
- -1 polysiloxane Polymers 0.000 title claims abstract description 34
- 239000000463 material Substances 0.000 title claims abstract description 24
- 230000003373 anti-fouling effect Effects 0.000 title claims abstract description 22
- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- 229920001296 polysiloxane Polymers 0.000 title claims abstract description 20
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 56
- 239000004593 Epoxy Substances 0.000 claims abstract description 36
- 239000007822 coupling agent Substances 0.000 claims abstract description 33
- ABTOQLMXBSRXSM-UHFFFAOYSA-N silicon tetrafluoride Chemical compound F[Si](F)(F)F ABTOQLMXBSRXSM-UHFFFAOYSA-N 0.000 claims abstract description 32
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical group [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims abstract description 29
- 239000000049 pigment Substances 0.000 claims abstract description 26
- 229910000077 silane Inorganic materials 0.000 claims abstract description 26
- 229920005989 resin Polymers 0.000 claims abstract description 18
- 239000011347 resin Substances 0.000 claims abstract description 18
- 239000002518 antifoaming agent Substances 0.000 claims abstract description 16
- 239000002270 dispersing agent Substances 0.000 claims abstract description 16
- 239000000945 filler Substances 0.000 claims abstract description 15
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 claims abstract description 10
- 238000004040 coloring Methods 0.000 claims abstract description 9
- 239000003960 organic solvent Substances 0.000 claims abstract description 9
- 239000000203 mixture Substances 0.000 claims description 30
- 238000000227 grinding Methods 0.000 claims description 17
- 239000000843 powder Substances 0.000 claims description 17
- 239000006185 dispersion Substances 0.000 claims description 14
- 229910021420 polycrystalline silicon Inorganic materials 0.000 claims description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 14
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 12
- 229910052760 oxygen Inorganic materials 0.000 claims description 12
- 239000001301 oxygen Substances 0.000 claims description 12
- 235000019441 ethanol Nutrition 0.000 claims description 11
- 238000010438 heat treatment Methods 0.000 claims description 11
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 10
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 10
- 238000003756 stirring Methods 0.000 claims description 10
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 9
- 238000002156 mixing Methods 0.000 claims description 8
- 229910052681 coesite Inorganic materials 0.000 claims description 7
- 229910052906 cristobalite Inorganic materials 0.000 claims description 7
- 239000010445 mica Substances 0.000 claims description 7
- 229910052618 mica group Inorganic materials 0.000 claims description 7
- DCKVNWZUADLDEH-UHFFFAOYSA-N sec-butyl acetate Chemical group CCC(C)OC(C)=O DCKVNWZUADLDEH-UHFFFAOYSA-N 0.000 claims description 7
- 239000000377 silicon dioxide Substances 0.000 claims description 7
- 229910052682 stishovite Inorganic materials 0.000 claims description 7
- 229910052905 tridymite Inorganic materials 0.000 claims description 7
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 6
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 6
- 150000001298 alcohols Chemical class 0.000 claims description 6
- 150000001335 aliphatic alkanes Chemical class 0.000 claims description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 6
- 230000008569 process Effects 0.000 claims description 6
- 239000004408 titanium dioxide Substances 0.000 claims description 6
- LRXTYHSAJDENHV-UHFFFAOYSA-H zinc phosphate Chemical compound [Zn+2].[Zn+2].[Zn+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O LRXTYHSAJDENHV-UHFFFAOYSA-H 0.000 claims description 6
- 229910000165 zinc phosphate Inorganic materials 0.000 claims description 6
- 229920000137 polyphosphoric acid Polymers 0.000 claims description 5
- 239000006229 carbon black Substances 0.000 claims description 4
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 claims description 4
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 4
- SNNDROOIGNHUBX-UHFFFAOYSA-N 3-(1,1-difluorooctoxy-methoxy-methylsilyl)propan-1-ol Chemical class FC(O[Si](OC)(C)CCCO)(CCCCCCC)F SNNDROOIGNHUBX-UHFFFAOYSA-N 0.000 claims description 3
- LMVLVUPTDRWATB-UHFFFAOYSA-N 3-[dimethoxy(methyl)silyl]propan-1-ol Chemical compound CO[Si](C)(OC)CCCO LMVLVUPTDRWATB-UHFFFAOYSA-N 0.000 claims description 3
- NYTYVZFFEIBDBZ-UHFFFAOYSA-N CO[SiH](OC)OC.[Ru].[F] Chemical class CO[SiH](OC)OC.[Ru].[F] NYTYVZFFEIBDBZ-UHFFFAOYSA-N 0.000 claims description 3
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 3
- 239000000470 constituent Substances 0.000 claims description 3
- ZTFZSHLWORMEHO-UHFFFAOYSA-A pentaaluminum;[oxido(phosphonatooxy)phosphoryl] phosphate Chemical compound [Al+3].[Al+3].[Al+3].[Al+3].[Al+3].[O-]P([O-])(=O)OP([O-])(=O)OP([O-])([O-])=O.[O-]P([O-])(=O)OP([O-])(=O)OP([O-])([O-])=O.[O-]P([O-])(=O)OP([O-])(=O)OP([O-])([O-])=O ZTFZSHLWORMEHO-UHFFFAOYSA-A 0.000 claims description 3
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 3
- JLGNHOJUQFHYEZ-UHFFFAOYSA-N trimethoxy(3,3,3-trifluoropropyl)silane Chemical compound CO[Si](OC)(OC)CCC(F)(F)F JLGNHOJUQFHYEZ-UHFFFAOYSA-N 0.000 claims description 3
- 229910052725 zinc Inorganic materials 0.000 claims description 3
- 239000011701 zinc Substances 0.000 claims description 3
- AYGUCHAPOTYFRT-UHFFFAOYSA-H zinc molybdenum(4+) diphosphate Chemical compound [Zn+2].[Mo+4].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O AYGUCHAPOTYFRT-UHFFFAOYSA-H 0.000 claims description 3
- XAEWLETZEZXLHR-UHFFFAOYSA-N zinc;dioxido(dioxo)molybdenum Chemical compound [Zn+2].[O-][Mo]([O-])(=O)=O XAEWLETZEZXLHR-UHFFFAOYSA-N 0.000 claims description 3
- FWGZLZNGAVBRPW-UHFFFAOYSA-N alumane;strontium Chemical compound [AlH3].[Sr] FWGZLZNGAVBRPW-UHFFFAOYSA-N 0.000 claims description 2
- GAURFLBIDLSLQU-UHFFFAOYSA-N diethoxy(methyl)silicon Chemical compound CCO[Si](C)OCC GAURFLBIDLSLQU-UHFFFAOYSA-N 0.000 claims description 2
- ZLGWXNBXAXOQBG-UHFFFAOYSA-N triethoxy(3,3,3-trifluoropropyl)silane Chemical compound CCO[Si](OCC)(OCC)CCC(F)(F)F ZLGWXNBXAXOQBG-UHFFFAOYSA-N 0.000 claims description 2
- BIFQHCGLXZWNLN-UHFFFAOYSA-N 2,2,6-trifluoro-4-methyl-4-propyl-1,3,5,2,4,6-trioxatrisilinane Chemical compound CCC[Si]1(C)O[SiH](F)O[Si](F)(F)O1 BIFQHCGLXZWNLN-UHFFFAOYSA-N 0.000 claims 1
- LLVCYRUMZGOZTD-UHFFFAOYSA-N 2-(trifluoromethoxyperoxy)pentane Chemical compound FC(OOOC(C)CCC)(F)F LLVCYRUMZGOZTD-UHFFFAOYSA-N 0.000 claims 1
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims 1
- QQQSFSZALRVCSZ-UHFFFAOYSA-N triethoxysilane Chemical compound CCO[SiH](OCC)OCC QQQSFSZALRVCSZ-UHFFFAOYSA-N 0.000 claims 1
- 238000005260 corrosion Methods 0.000 abstract description 21
- 230000007797 corrosion Effects 0.000 abstract description 15
- 239000007787 solid Substances 0.000 abstract description 10
- 238000005516 engineering process Methods 0.000 abstract description 4
- 239000002105 nanoparticle Substances 0.000 abstract 1
- 238000012360 testing method Methods 0.000 description 15
- 239000003973 paint Substances 0.000 description 13
- 229920005591 polysilicon Polymers 0.000 description 10
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 description 6
- 229910052751 metal Inorganic materials 0.000 description 6
- 239000002184 metal Substances 0.000 description 6
- 150000003839 salts Chemical class 0.000 description 6
- 238000007599 discharging Methods 0.000 description 5
- 238000001914 filtration Methods 0.000 description 5
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 5
- 239000007921 spray Substances 0.000 description 5
- 239000000758 substrate Substances 0.000 description 5
- 230000008859 change Effects 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 125000003700 epoxy group Chemical group 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 238000005259 measurement Methods 0.000 description 4
- 230000032683 aging Effects 0.000 description 3
- 238000004132 cross linking Methods 0.000 description 3
- 238000005507 spraying Methods 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 239000012752 auxiliary agent Substances 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000007935 neutral effect Effects 0.000 description 2
- 231100000252 nontoxic Toxicity 0.000 description 2
- 230000003000 nontoxic effect Effects 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000002966 varnish Substances 0.000 description 2
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 description 1
- MTEZSDOQASFMDI-UHFFFAOYSA-N 1-trimethoxysilylpropan-1-ol Chemical compound CCC(O)[Si](OC)(OC)OC MTEZSDOQASFMDI-UHFFFAOYSA-N 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 238000007605 air drying Methods 0.000 description 1
- ILRRQNADMUWWFW-UHFFFAOYSA-K aluminium phosphate Chemical compound O1[Al]2OP1(=O)O2 ILRRQNADMUWWFW-UHFFFAOYSA-K 0.000 description 1
- 229940001007 aluminium phosphate Drugs 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- RLQHVRXAJUWMRL-UHFFFAOYSA-K aluminum;strontium;phosphate Chemical compound [Al+3].[Sr+2].[O-]P([O-])([O-])=O RLQHVRXAJUWMRL-UHFFFAOYSA-K 0.000 description 1
- 230000003712 anti-aging effect Effects 0.000 description 1
- 230000002421 anti-septic effect Effects 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000001680 brushing effect Effects 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 235000013339 cereals Nutrition 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 238000005034 decoration Methods 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- NZZFYRREKKOMAT-UHFFFAOYSA-N diiodomethane Chemical compound ICI NZZFYRREKKOMAT-UHFFFAOYSA-N 0.000 description 1
- 238000003618 dip coating Methods 0.000 description 1
- 230000003628 erosive effect Effects 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 230000008595 infiltration Effects 0.000 description 1
- 238000001764 infiltration Methods 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 229910001092 metal group alloy Inorganic materials 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- GOWYWDDPOBCVFH-UHFFFAOYSA-N methoxy-methyl-propyl-(trifluoromethoxy)silane Chemical compound FC(O[Si](OC)(C)CCC)(F)F GOWYWDDPOBCVFH-UHFFFAOYSA-N 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 238000010422 painting Methods 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 230000037452 priming Effects 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 238000005488 sandblasting Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 229920002050 silicone resin Polymers 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- YUYCVXFAYWRXLS-UHFFFAOYSA-N trimethoxysilane Chemical compound CO[SiH](OC)OC YUYCVXFAYWRXLS-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Paints Or Removers (AREA)
- Application Of Or Painting With Fluid Materials (AREA)
Abstract
The present invention relates to nanometer particle-modified technology and coating technology, specially a kind of antifouling anticorrosive nano polysiloxane coating materials of primer-topcoat in one and preparation method thereof.Firstly, the epoxy functionality for carrying out nanoparticle is silane coupler modified and silicon fluoride is coupling agent modified.Then, in terms of mass fraction, 40~60 parts of polyorganosiloxane resin are taken, the silane coupler modified Nano-meter SiO_2 of epoxy functionality20.2~1 part；The coupling agent modified Nano-meter SiO_2 of silicon fluoride20.2~1 part；0.5~1.5 part of anti-settling agent；0.3~0.8 part of levelling agent；0.2~0.7 part of defoaming agent；0.4~1 part of dispersing agent；5~10 parts of coloring pigment；20~30 parts of rust resisting pigment；5~15 parts of filler；3~8 parts of organic solvent, disperses, is ground to 30 μm of fineness hereinafter, first component is made；First component is mixed with second component again, is prepared into antifouling anticorrosive nano polysiloxane coating materials.This coating has the feature of high solid, has outstanding corrosion-resistant, weather-proof, contaminated resistance, the corrosion-resistant field suitable for a variety of occasions.
Description
Technical field
The present invention relates to nanometer particle-modified technology and coating technology, specially a kind of antifouling anticorrosive nano of primer-topcoat in one
Polysiloxane coating materials and preparation method thereof, this coating can be used for ship, ocean platform, terminal facilities, bridge, vehicle, aviation,
Electric power facility etc., while there is antifouling and anti-corrosion function.
Background technique
The continuous development of modern industrialization makes to corrode and pollute all constantly aggravating.The whole world is every year because metal erosion is made
At direct economic loss about 700,000,000,000 U.S. dollars.According to statistics, China every year because corrosion caused by loss account for about GDP 3~
5%.Currently, loss caused by corrosion is far longer than the summation of natural calamity and all kinds of causality losses more than 2 trillion yuans.Therefore,
For metal material various anticorrosive measures application be the key that reduce corrosion loss, these measures include prepare it is anti-corrosion
Metal alloy carries out Treatment of Metal Surface and modification, using corrosion inhibitor, coating organic coating and using cathode protection measure
Deng.Wherein, organic coating be it is a kind of extremely commonly protect the metal from corrosion means (account for the 70% of metal protection means with
On).
Traditional solvent based coating can generate volatile organic matter during production and use.To eliminate paint spraying
Pollution to atmosphere, anticorrosive paint hydropositive, high solid direction are developed, to replace solvent type anticorrosive paint.High solid
Part is because of its pigments and fillers large percentage, and waterborne coatings are because it generates channel in the curing process, both coating are in metal surface
The coating of formation easily forms high porosity, fast so as to cause corrosive medium infiltration rate.Therefore, the hole of coating how is reduced
Rate further increases the corrosion resistance of coating, is always academia and the direction that industry is made great efforts.
After coating resin matrix immobilization, using nanometer pigments and fillers, it can be substantially reduced the porosity of coating, reduce corrosion
The transmission rate of medium.Under normal conditions, nanometer pigments and fillers exist in a manner of physics filling, in nanometer pigments and fillers and tree
The interface of aliphatic radical matter, there are still slight voids.If nanometer pigments and fillers are realized and the combination of resin matrix, especially chemistry is tied
It closes, then can improve the compactness of coating, and then improve the Corrosion Protection of coating.However, about chemical surface modification nanometer face
Filler, and be used for preparing highly corrosion resistant coating, but seldom see relevant report.
Summary of the invention
The object of the present invention is to provide a kind of corrosion resistance, anti-pollution and the strong primer-topcoat in one of anti-aging property are anti-
Dirty anticorrosive nano polysiloxane coating materials and preparation method thereof, meet ship, ocean platform, terminal facilities, bridge, vehicle, aviation,
Electric power facility etc. is antifouling and anti-corrosion function requires.
In order to achieve the above object, the technical scheme is that
A kind of antifouling anticorrosive nano polysiloxane coating materials of primer-topcoat in one, which is two groups of first, second and is grouped as, by quality
Number meter, specific formula are as follows:
(1) first component
(2) second component: curing agent；
First component and second constituent mass ratio are 100:(12~20).
The antifouling anticorrosive nano polysiloxane coating materials of the primer-topcoat in one, polyorganosiloxane resin are poly- for Silikopon EF
Silicone resin；Anti-settling agent is Anti-settling agent 202P anti-settling agent, and levelling agent is Tego Flow 300 or BYK-
306 levelling agents, defoaming agent are 530 defoaming agent of Tego 936 or BYK-A, and dispersing agent is Tego 670 or BYK-163 dispersing agent；
Coloring pigment is the one or two of titanium dioxide and carbon black；Rust resisting pigment is trbasic zinc phosphate, pucherite, zinc molybdate, molybdenum phosphate zinc, three
The one or more of poly aluminium phosphate, polyphosphoric acids aluminium strontium, polyphosphoric acids zinc；Filler is 325 mesh mica powders；Organic solvent is
Butyl ester；Curing agent is amino silicane coupling agent.
The antifouling anticorrosive nano polysiloxane coating materials of the primer-topcoat in one, Nano-meter SiO_22Method of modifying it is as follows:
1) Nano-meter SiO_22The silane coupler modified process of epoxy functionality
By Nano-meter SiO_22It is added in epoxy functionality silane coupling agent, makes Nano-meter SiO_22Mass fraction be 20%~
30%；Add Nano-meter SiO_22The water and 40~50 times of alcohols that 40~50 times of quality, prepare resulting mixture；Mixture 60~
1~2h of heating stirring under the conditions of 100 DEG C and subacidity pH=4.5~5.5；Finally, mixture is dried under the conditions of 30~50 DEG C；
After grinding, 325 meshes are crossed, obtain the silane coupler modified Nano-meter SiO_2 of epoxy functionality2Powder；
2) Nano-meter SiO_22The coupling agent modified process of silicon fluoride
By Nano-meter SiO_22It is added in silicon fluoride coupling agent, makes Nano-meter SiO_22Mass fraction be 20%~30%；It adds
Nano-meter SiO_22The water and 3~6 times of alcohols that 40~50 times of quality, prepare resulting mixture；Mixture is in 60~100 DEG C and subacidity
0.5~2h of heating stirring under the conditions of pH=4.5~5.5；Finally, mixture is dried under the conditions of 30~50 DEG C；After grinding, mistake
325 meshes obtain the coupling agent modified Nano-meter SiO_2 of silicon fluoride2Powder.
The antifouling anticorrosive nano polysiloxane coating materials of the primer-topcoat in one, alcohols be methanol, ethyl alcohol, propyl alcohol, ethylene glycol,
One kind of isopropanol or isobutanol.
The antifouling anticorrosive nano polysiloxane coating materials of the primer-topcoat in one, Nano-meter SiO_22Modified epoxy functional used
Group's silane coupling agent is 3- glycidyl ether oxypropyltrimethoxysilane, 3- glycydoxy triethoxysilicane
Alkane, 3- (the third oxygen of 2,3- epoxy) hydroxypropyl methyl dimethoxysilane, 3- glycydoxy methyldiethoxysilane,
One kind of epoxy group trimethoxy silane and γ-(2,3- the third oxygen of epoxy) propyl trimethoxy silicane.
The antifouling anticorrosive nano polysiloxane coating materials of the primer-topcoat in one, Nano-meter SiO_22Modified silicon fluoride coupling used
Agent is 17 fluorine ruthenium trimethoxysilanes, trifluoro propyl methyl dimethoxysilane, trifluoro propyl trimethoxy silane, (N-
Perfluorooctyl sulfonyl)-aminopropyl triethoxysilane, tridecafluoro-n-octyltriethoxysilane, three silicon of trifluoro propyl methyl ring
Oxygen alkane, trifluoro propyl triethoxysilane, ten fluoroalkyl trimethoxy silanes, ten difluoro heptyl hydroxypropyl methyl dimethoxy silicon
One kind of alkane.
The preparation method of the antifouling anticorrosive nano polysiloxane coating materials of the primer-topcoat in one, the preparation method is as follows:
By polyorganosiloxane resin, the silane coupler modified Nano-meter SiO_2 of epoxy functionality2, silicon fluoride is coupling agent modified receives
Rice SiO2, anti-settling agent, levelling agent, defoaming agent, dispersing agent, coloring pigment, rust resisting pigment, filler and organic solvent mixing, with height
800~1500 revs/min of fast dispersion machine high speed dispersion 10~30 minutes, then with ball mill grinding 4~8 hours, obtaining fineness was 30 μ
M is hereinafter, be made first component；Second curing components agent is added, is stirred evenly, the poly- silicon oxygen of the antifouling anticorrosive nano of primer-topcoat in one is made
Alkane coating.
It advantages of the present invention and has the beneficial effect that:
1, the present invention relates to prepare and use nanometer particle-modified technique.Firstly, silane coupled by epoxy functionality
Agent modified Nano SiO2With the coupling agent modified Nano-meter SiO_2 of silicon fluoride2.Both front and back modified Nano SiO2It is respectively used to increase poly- silicon
The anti-corrosion and anti-pollution function of siloxane paint.The principle for improving antiseptic property is to utilize Nano-meter SiO_22The polyhydroxy characteristic on surface,
Grafting has the silane coupling agent of epoxy group.When amino silicane coupling agent (curing agent) and the Silikopon EF for having epoxy group
It, also can be with the modified Nano SiO with epoxy group while polyorganosiloxane resin crosslinking curing2Crosslinking, to make Nano-meter SiO_22
Chemical bonding is generated with resinous substrates, increases the consistency of coating, improves the corrosion resistance of coating.Improve the original of anti-pollution
Reason is to be grafted the Nano-meter SiO_2 of silicon fluoride2It is filled in coating, the coating surface after crosslinking curing forms the essence of micron-nanometer
Fine texture, the coupling agent modified Nano-meter SiO_2 of silicon fluoride2There is strong hydrophobic effect to reach to realize the low-surface-energy of coating for itself
To anti-fouling effect.
2, coating of the present invention uses nontoxic rust resisting pigment completely, safety, environmental protection.Coating has excellent corrosion resistant
Corrosion, resistance to ag(e)ing, humidity resistance and anti-pollution.
3, coating of the present invention is a kind of primer-topcoat in one high solid coating, solid content > 90wt.%.Coating
Anti-corrosion function possessed by existing priming paint also has anti-pollution function and decoration functions possessed by finishing coat.It is required according to anticorrosion, it can
Coating thickness is 20~100 μm, reduces spraying road number, improves construction efficiency, reduce cost.
Specific embodiment
In a specific embodiment, the antifouling anticorrosive nano polysiloxane coating materials of primer-topcoat in one of the present invention are two groups of first, second
It is grouped as, according to the mass fraction, specific formula is as follows:
(1) first component
40~60 parts of polyorganosiloxane resin (preferably 45~55 parts), the silane coupler modified Nano-meter SiO_2 of epoxy functionality2
0.2~1 part (preferably 0.3~0.6 part), the coupling agent modified Nano-meter SiO_2 of silicon fluoride20.2~1 part (preferably 0.3~0.6 part), prevent
Heavy 0.5~1.5 part of agent (preferably 0.8~1.2 part), 0.3~0.8 part of levelling agent (preferably 0.4~0.6 part), defoaming agent 0.2~
0.7 part (preferably 0.3~0.6 part), 0.4~1 part of dispersing agent (preferably 0.5~0.7 part), 5~10 parts (preferably 6~8 of coloring pigment
Part), 20~30 parts of rust resisting pigment (preferably 22~28 parts), 5~15 parts of filler (preferably 8~12 parts), 3~8 parts of organic solvent are (excellent
Select 3~6 parts)；
(2) second component: curing agent；
First component: second constituent mass ratio is 100:(12~20).
Wherein, polyorganosiloxane resin can be the Silikopon EF polyorganosiloxane resin of German Degussa；Nano-meter SiO_22?
Grain partial size is 20~30nm；Auxiliary agent is common auxiliary agent in coating.Wherein, levelling agent can be Tego Flow300 or BYK-306
Levelling agent, dispersing agent can be Tego 670 or BYK-163 dispersing agent, and defoaming agent can be 530 defoaming agent of Tego 936 or BYK-A,
Anti-settling agent can be Anti-settling agent 202P anti-settling agent；Coloring pigment is the one or two of titanium dioxide and carbon black,
The granularity level of pigment is micron order；Rust resisting pigment is trbasic zinc phosphate, pucherite, zinc molybdate, molybdenum phosphate zinc, aluminium triphosphate, more
The one or more of poly aluminium phosphate strontium, polyphosphoric acids zinc；Filler is 325 mesh mica powders；Organic solvent is butyl ester；Curing agent
It can be German Degussa Dynasylan AEMO amino curing agent or 3-aminopropyltriethoxysilane.
The above-mentioned antifouling anticorrosive nano polysiloxane coating materials of primer-topcoat in one to make and use process as follows:
1) epoxy functionality silane coupling agent Nano-meter SiO_2 is prepared2With the coupling agent modified Nano-meter SiO_2 of silicon fluoride2, by poly- silicon
Oxygen alkane resin, the silane coupler modified Nano-meter SiO_2 of epoxy functionality2, the coupling agent modified Nano-meter SiO_2 of silicon fluoride2, anti-settling agent, stream
Flat agent, defoaming agent, dispersing agent, coloring pigment, rust resisting pigment, filler and organic solvent mixing, with high speed disperser 800~1500
Revs/min high speed dispersion 10~30 minutes；
2) above-mentioned material with ball mill grinding 4~8 hours, test fineness reaches 30 μm hereinafter, discharging, filtering, obtain
Component one；
3) component two (curing agent) is added in component one, after mixing evenly, spraying, brushing or dip-coating are in metal base
Surface, room temperature or heating cure form primer-topcoat in one nano polysilicon oxygen alkane coating.
Test plate (panel) preparation method: several 150mm × 75mm × 2mm Q235 surface of steel plate is after sandblasting, oil removal treatment, spray
(thickness of dry film is 70 μm) together is applied, after air drying 7 days, carries out the relevant performance test of coating.
The neutral salt spray test of coating sample uses the YWQ type salt fog of Jiangsu Huaian Central Asia testing equipment Co., Ltd production
Case.NaCl solution concentration 5wt.%, test temperature are 35 ± 2 DEG C.It is that ASTM B117 paint film is resistance to that neutral salt spray test, which executes standard,
Salt fog measuring method evaluates coating salt spray resistance grade according to GB1740-79.
The damp heat test of coating sample uses the GDJS-225 type moisture-heat test-box of Jiangsu Ai Mosheng instrument company production.It is wet
Hot the temperature inside the box is (47 ± 1) DEG C, and relative humidity is (96 soil 2) %.The standard that damp heat test executes is ISO 6270-1 colored paint
With the measurement of varnish moisture-proof.
The degradation of coating sample is ultraviolet using the ZN-P type of Jiangsu Ai Mosheng test apparatus Be Able LLC production
Light aging test case.Fluorescent ultraviolet lamp is light source (UVA model lamp source), by GB/T 1766-2008 standard colored paint and varnish coat
The ranking method of aging can be carried out assessment to coating resistance to ag(e)ing.
The water contact angle test of coating sample is carried out using water contact angle measurement instrument (JC2000D2, Powereach company)
Measurement is 2 μ L for the water of measurement and the amount of diiodomethane.
In the following, being further elaborated on by embodiment to the present invention.
Embodiment 1
1, the silane coupler modified Nano-meter SiO_2 of epoxy functionality2With the coupling agent modified Nano-meter SiO_2 of silicon fluoride2Preparation
1) the silane coupler modified Nano-meter SiO_2 of epoxy functionality2
By Nano-meter SiO_22It is added in 3- glycidyl ether oxypropyltriethoxysilane, makes Nano-meter SiO_22Quality point
Number is 20%；Add Nano-meter SiO_22The water and 40 times of isopropanol that 40 times of quality, prepare resulting mixture.Mixture at 80 DEG C and
Heating stirring 1h under the conditions of subacidity (pH=5).Finally, mixture is dried under the conditions of 30 DEG C.After grinding, 325 meshes are crossed, are obtained
Obtain the silane coupler modified Nano-meter SiO_2 of epoxy functionality2Powder.
2) the coupling agent modified Nano-meter SiO_2 of silicon fluoride2
By Nano-meter SiO_22It is added in 17 fluorine ruthenium trimethoxysilanes, makes Nano-meter SiO_22Mass fraction be 20%；Again
Nano-meter SiO_2 is added2The water and 3 times of ethyl alcohol that 40 times of quality, prepare resulting mixture.Mixture is in 80 DEG C and subacidity (pH=5)
Under the conditions of heating stirring 1h.Finally, mixture is dried under the conditions of 30 DEG C.After grinding, 325 meshes are crossed, obtain silicon fluoride coupling
Agent modified Nano SiO2Powder.
2, the preparation of primer-topcoat in one nano polysilicon siloxane paint
The preparation method of first component: according to the mass fraction, Silikopon EF polyorganosiloxane resin is added in dispersion cylinder
45 parts, the silane coupler modified Nano-meter SiO_2 of epoxy functionality20.5 part, the coupling agent modified Nano-meter SiO_2 of silicon fluoride20.5 part,
1 part of anti-settling agent (Anti-settling agent 202P), 0.5 part of levelling agent (BYK-306), defoaming agent (BYK-A 530) 0.5
Part, 0.5 part of dispersing agent (BYK-163), 9.5 parts of titanium dioxide, 26 parts of trbasic zinc phosphate, 11 parts of mica powder, 5 parts of butyl ester.Above-mentioned material exists
Then 800~1500 revs/min high speed dispersion 10~30 minutes in high speed disperser are used ball mill grinding 4~8 hours, test is thin
Degree reaches 30 μm hereinafter, discharging, filtering, obtain first component；
Second group is divided into Dynasylan AEMO amino curing agent.
First component and second component are mixed in the ratio of 100:14, after mixing evenly, are sprayed on Q235 substrate surface, room temperature is solid
Change drying 7 days, form primer-topcoat in one nano polysilicon oxygen alkane coating, thickness of dry film is 70 μm.
Embodiment 2
1, the silane coupler modified Nano-meter SiO_2 of epoxy functionality2With the coupling agent modified Nano-meter SiO_2 of silicon fluoride2Preparation
1) the silane coupler modified Nano-meter SiO_2 of epoxy functionality2
By Nano-meter SiO_22It is added in 3- (2,3- the third oxygen of epoxy) hydroxypropyl methyl dimethoxysilane, makes Nano-meter SiO_22Matter
Measuring score is 25%；Add Nano-meter SiO_22The water and 50 times of isopropanol that 45 times of quality, prepare resulting mixture.Mixture exists
Heating stirring 0.5h under the conditions of 100 DEG C and subacidity (pH=5.5).Finally, mixture is dried under the conditions of 40 DEG C.After grinding,
325 meshes are crossed, the silane coupler modified Nano-meter SiO_2 of epoxy functionality is obtained2Powder.
2) the coupling agent modified Nano-meter SiO_2 of silicon fluoride2
By Nano-meter SiO_22It is added in ten difluoro heptyl hydroxypropyl methyl dimethoxysilanes, makes Nano-meter SiO_22Mass fraction
It is 25%；Add Nano-meter SiO_22The water and 5 times of ethyl alcohol that 45 times of quality, prepare resulting mixture.Mixture is at 100 DEG C and slightly sour
Heating stirring 0.5h under the conditions of property (pH=5.5).Finally, mixture is dried under the conditions of 40 DEG C.After grinding, 325 meshes are crossed, are obtained
Obtain the coupling agent modified Nano-meter SiO_2 of silicon fluoride2Powder.
2, the preparation of primer-topcoat in one nano polysilicon siloxane paint
The preparation method of first component: according to the mass fraction, Silikopon EF polyorganosiloxane resin is added in dispersion cylinder
50 parts, the silane coupler modified Nano-meter SiO_2 of epoxy functionality20.8 part, the coupling agent modified Nano-meter SiO_2 of silicon fluoride20.2 part,
1 part of anti-settling agent (Anti-settling agent 202P), 0.5 part of levelling agent (Tego Flow 300), defoaming agent (Tego
936) 0.5 part, 0.5 part of dispersing agent (Tego 670), 6.5 parts of carbon black, 23 parts of aluminium triphosphate, 14 parts of mica powder, 3 parts of butyl ester.
Above-mentioned material 800~1500 revs/min high speed dispersion 10~30 minutes in high speed disperser, it is then small with ball mill grinding 4~8
When, test fineness reaches 30 μm hereinafter, discharging, filtering, obtain first component；
Second group is divided into Dynasylan AEMO amino curing agent.
First component and second component are mixed in the ratio of 100:13, after mixing evenly, are sprayed on Q235 substrate surface, room temperature is solid
Change drying 7 days, form primer-topcoat in one nano polysilicon oxygen alkane coating, thickness of dry film is 70 μm.
Embodiment 3
1, the silane coupler modified Nano-meter SiO_2 of epoxy functionality2With the coupling agent modified Nano-meter SiO_2 of silicon fluoride2Preparation
1) the silane coupler modified Nano-meter SiO_2 of epoxy functionality2
By Nano-meter SiO_22It is added in γ-(2,3- the third oxygen of epoxy) propyl trimethoxy silicane, makes Nano-meter SiO_22Quality point
Number is 30%；Add Nano-meter SiO_22The water and 45 times of isopropanol that 50 times of quality, prepare resulting mixture.Mixture at 90 DEG C and
Heating stirring 2h under the conditions of subacidity (pH=4.5).Finally, mixture is dried under the conditions of 50 DEG C.After grinding, 325 meshes are crossed,
Obtain the silane coupler modified Nano-meter SiO_2 of epoxy functionality2Powder.
2) the coupling agent modified Nano-meter SiO_2 of silicon fluoride2
By Nano-meter SiO_22It is added in trifluoro propyl trimethoxy silane, makes Nano-meter SiO_22Mass fraction be 30%；Again plus
Enter Nano-meter SiO_22The water and 4 times of ethyl alcohol that 50 times of quality, prepare resulting mixture.Mixture is in 90 DEG C and subacidity (pH=4.5)
Under the conditions of heating stirring 2h.Finally, mixture is dried under the conditions of 50 DEG C.After grinding, 325 meshes are crossed, obtain silicon fluoride coupling
Agent modified Nano SiO2Powder.
2, the preparation of primer-topcoat in one nano polysilicon siloxane paint
The preparation method of first component: according to the mass fraction, Silikopon EF polyorganosiloxane resin is added in dispersion cylinder
55 parts, the silane coupler modified Nano-meter SiO_2 of epoxy functionality20.4 part, the coupling agent modified Nano-meter SiO_2 of silicon fluoride20.6 part,
1 part of anti-settling agent (Anti-settling agent 202P), 0.5 part of levelling agent (BYK-306), defoaming agent (BYK-A 530) 0.5
Part, 0.5 part of dispersing agent (BYK-163), 7.5 parts of titanium dioxide, 22 parts of trbasic zinc phosphate, 8 parts of mica powder, 4 parts of butyl ester.Above-mentioned material is in height
Then 800~1500 revs/min high speed dispersion 10~30 minutes in fast dispersion machine are used ball mill grinding 4~8 hours, fineness is tested
Reach 30 μm hereinafter, discharging, filtering, obtain first component；
Second group is divided into Dynasylan AEMO amino curing agent.
First component and second component are mixed in the ratio of 100:15, after mixing evenly, are sprayed on Q235 substrate surface, room temperature is solid
Change drying 7 days, form primer-topcoat in one nano polysilicon oxygen alkane coating, thickness of dry film is 70 μm.
Comparative example 1
The preparation method of first component: according to the mass fraction, Silikopon EF polyorganosiloxane resin is added in dispersion cylinder
45 parts, 1 part of anti-settling agent (Anti-settling agent 202P), 0.5 part of levelling agent (BYK-306), defoaming agent (BYK-A
530) 0.5 part, 0.5 part of dispersing agent (BYK-163) is 9.5 parts of titanium dioxide, 27 parts of trbasic zinc phosphate, 11 parts of mica powder, 5 parts of butyl ester, above-mentioned
Then material 800~1500 revs/min high speed dispersion 10~30 minutes in high speed disperser are used ball mill grinding 4~8 hours,
Test fineness reaches 30 μm hereinafter, discharging, filtering, obtain first component；
Second group is divided into Dynasylan AEMO amino curing agent.
First component and second component are mixed in the ratio of 100:14, after mixing evenly, are sprayed on Q235 substrate surface, room temperature is solid
Change drying 7 days, form primer-topcoat in one nano polysilicon oxygen alkane coating, thickness of dry film is 70 μm.
Examples 1 to 3 and the test result of comparative example 1 are as follows:
The performance of 1 bottom surface of table unification polysiloxane coating materials
| Salt spray resistance (h) | Wet-heat resisting (h) | Ageing-resistant (h) | Water contact angle (°) | |
| Embodiment 1 | 4000 | 4000 | 1000 | 101 |
| Embodiment 2 | 4500 | 4200 | 1000 | 96 |
| Embodiment 3 | 3700 | 3600 | 1000 | 105 |
| Comparative example 1 | 3300 | 3400 | 1000 | 90 |
Embodiment and comparative example the result shows that, the present invention proposes to develop the nano polysilicon siloxane paint of bottom surface unification, leads to
Cross the silane coupler modified Nano-meter SiO_2 of addition epoxy functionality2With the coupling agent modified Nano-meter SiO_2 of silicon fluoride2, polysiloxanes painting
The anti-corrosion and anti-pollution of layer are improved.Coating uses nontoxic environment-friendly antirust pigment, and nano polysilicon siloxane paint
The coating of feature with high solid, preparation is conducive to environmental protection.
Claims (3)
1. a kind of antifouling anticorrosive nano polysiloxane coating materials of primer-topcoat in one, which is characterized in that the coating is the two groups of groupings of first, second
At according to the mass fraction, specific formula is as follows:
(1) first component
40~60 parts of polyorganosiloxane resin；
The silane coupler modified Nano-meter SiO_2 of epoxy functionality20.2~1.0 part；
The coupling agent modified Nano-meter SiO_2 of silicon fluoride20.2~1.0 part；
0.5~1.5 part of anti-settling agent；
0.3~0.8 part of levelling agent；
0.2~0.7 part of defoaming agent；
0.4~1.0 part of dispersing agent；
5~10 parts of coloring pigment；
20~30 parts of rust resisting pigment；
5~15 parts of filler；
3~8 parts of organic solvent；
(2) second component: curing agent；
First component and second constituent mass ratio are 100:(12~20)；
Wherein, Nano-meter SiO_22Method of modifying it is as follows:
1) Nano-meter SiO_22The silane coupler modified process of epoxy functionality
By Nano-meter SiO_22It is added in epoxy functionality silane coupling agent, makes Nano-meter SiO_22Mass fraction be 20%~30%；Again
Nano-meter SiO_2 is added2The water and 40~50 times of alcohols that 40~50 times of quality, prepare resulting mixture；Mixture is at 60~100 DEG C
With 1~2 h of heating stirring under the conditions of subacidity pH=4.5~5.5；Finally, mixture is dried under the conditions of 30~50 DEG C；Grinding
Afterwards, 325 meshes are crossed, the silane coupler modified Nano-meter SiO_2 of epoxy functionality is obtained2Powder；
2) Nano-meter SiO_22The coupling agent modified process of silicon fluoride
By Nano-meter SiO_22It is added in silicon fluoride coupling agent, makes Nano-meter SiO_22Mass fraction be 20%~30%；Add nanometer
SiO2The water and 3~6 times of alcohols that 40~50 times of quality, prepare resulting mixture；Mixture 60~100 DEG C and subacidity pH=
0.5~2 h of heating stirring under the conditions of 4.5~5.5；Finally, mixture is dried under the conditions of 30~50 DEG C；After grinding, 325 are crossed
Mesh obtains the coupling agent modified Nano-meter SiO_2 of silicon fluoride2Powder；
Nano-meter SiO_22Modified epoxy functionality silane coupling agent used is 3- glycydoxy triethoxysilicane
Alkane, 3- (the third oxygen of 2,3- epoxy) hydroxypropyl methyl dimethoxysilane, 3- glycydoxy methyldiethoxysilane
With one kind of γ-(2,3- the third oxygen of epoxy) propyl trimethoxy silicane；
Nano-meter SiO_22Modified silicon fluoride coupling agent used is 17 fluorine ruthenium trimethoxysilanes, trifluoro propyl methyl dimethoxy oxygen
Base silane, trifluoro propyl trimethoxy silane, (N- perfluorooctyl sulfonyl)-aminopropyl triethoxysilane, ten trifluoro octyls
Triethoxysilane, trifluoro propyl methyl cyclotrisiloxane, trifluoro propyl triethoxysilane, ten fluoroalkyl trimethoxy silicon
One kind of alkane, ten difluoro heptyl hydroxypropyl methyl dimethoxysilanes；
Polyorganosiloxane resin is Silikopon EF polyorganosiloxane resin；Anti-settling agent is anti-for Anti-settling agent 202P
Heavy agent, levelling agent are Tego Flow 300 or BYK-306 levelling agent, and defoaming agent is 530 defoaming agent of Tego 936 or BYK-A,
Dispersing agent is Tego 670 or BYK-163 dispersing agent；Coloring pigment is the one or two of titanium dioxide and carbon black；Rust resisting pigment is
The one or two of trbasic zinc phosphate, pucherite, zinc molybdate, molybdenum phosphate zinc, aluminium triphosphate, polyphosphoric acids aluminium strontium, polyphosphoric acids zinc
More than；Filler is 325 mesh mica powders；Organic solvent is butyl ester；Curing agent is amino silicane coupling agent.
2. the antifouling anticorrosive nano polysiloxane coating materials of primer-topcoat in one according to claim 1, which is characterized in that alcohols is
One kind of methanol, ethyl alcohol, propyl alcohol, ethylene glycol, isopropanol or isobutanol.
3. the preparation method of the antifouling anticorrosive nano polysiloxane coating materials of primer-topcoat in one described in a kind of one of claim 1 to 2,
It is characterized in that, the preparation method is as follows:
By polyorganosiloxane resin, the silane coupler modified Nano-meter SiO_2 of epoxy functionality2, the coupling agent modified nanometer of silicon fluoride
SiO2, anti-settling agent, levelling agent, defoaming agent, dispersing agent, coloring pigment, rust resisting pigment, filler and organic solvent mixing, with high speed
800~1500 revs/min of dispersion machine high speed dispersion 10~30 minutes, then with ball mill grinding 4~8 hours, obtaining fineness was 30 μm
Hereinafter, first component is made；Second curing components agent is added, is stirred evenly, the poly- silicon oxygen of the antifouling anticorrosive nano of primer-topcoat in one is made
Alkane coating.
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| CN107760065A (en) * | 2017-09-22 | 2018-03-06 | 国网山东省电力公司电力科学研究院 | A kind of method of modifying of super-hydrophobic filler grain for antifouling flush paint and application |
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| CN111171719A (en) * | 2020-03-24 | 2020-05-19 | 常州天瑞新材料科技有限公司 | Anticorrosive nano ceramic coating for carbon steel and preparation method thereof |
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| CN115851023A (en) * | 2022-12-30 | 2023-03-28 | 无锡华东锌盾科技有限公司 | Solvent-free heavy-duty anticorrosive primer-topcoat coating and preparation method thereof |
| CN117363212B (en) * | 2023-11-01 | 2024-05-17 | 常熟理工学院 | Organic silicon marine antifouling paint based on affinity synergistic effect |
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