CN116285590A - Fluorinated silica/water-based epoxy resin composite anticorrosive paint and preparation method thereof - Google Patents
Fluorinated silica/water-based epoxy resin composite anticorrosive paint and preparation method thereof Download PDFInfo
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- 239000003822 epoxy resin Substances 0.000 title claims abstract description 99
- 229920000647 polyepoxide Polymers 0.000 title claims abstract description 99
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical class O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 title claims abstract description 83
- 239000002131 composite material Substances 0.000 title claims abstract description 73
- 239000003973 paint Substances 0.000 title claims abstract description 59
- 238000002360 preparation method Methods 0.000 title claims abstract description 39
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 38
- 239000004005 microsphere Substances 0.000 claims abstract description 48
- XDLMVUHYZWKMMD-UHFFFAOYSA-N 3-trimethoxysilylpropyl 2-methylprop-2-enoate Chemical compound CO[Si](OC)(OC)CCCOC(=O)C(C)=C XDLMVUHYZWKMMD-UHFFFAOYSA-N 0.000 claims abstract description 25
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 24
- DEQJNIVTRAWAMD-UHFFFAOYSA-N 1,1,2,4,4,4-hexafluorobutyl prop-2-enoate Chemical compound FC(F)(F)CC(F)C(F)(F)OC(=O)C=C DEQJNIVTRAWAMD-UHFFFAOYSA-N 0.000 claims abstract description 22
- 238000001914 filtration Methods 0.000 claims abstract description 18
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 15
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 126
- 239000002105 nanoparticle Substances 0.000 claims description 36
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical group N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 claims description 30
- 238000006243 chemical reaction Methods 0.000 claims description 29
- 238000003756 stirring Methods 0.000 claims description 24
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 18
- 238000010992 reflux Methods 0.000 claims description 14
- 238000001035 drying Methods 0.000 claims description 13
- 239000003999 initiator Substances 0.000 claims description 12
- 238000006116 polymerization reaction Methods 0.000 claims description 12
- 239000005543 nano-size silicon particle Substances 0.000 claims description 10
- 235000012239 silicon dioxide Nutrition 0.000 claims description 10
- 239000004744 fabric Substances 0.000 claims description 9
- 238000000034 method Methods 0.000 claims description 9
- 229910052757 nitrogen Inorganic materials 0.000 claims description 9
- 239000000080 wetting agent Substances 0.000 claims description 7
- 239000000758 substrate Substances 0.000 claims description 6
- 239000002518 antifoaming agent Substances 0.000 claims description 5
- 238000005406 washing Methods 0.000 claims description 5
- 230000009471 action Effects 0.000 claims description 2
- 238000009210 therapy by ultrasound Methods 0.000 claims description 2
- 239000013530 defoamer Substances 0.000 claims 2
- 238000004519 manufacturing process Methods 0.000 claims 1
- 239000002904 solvent Substances 0.000 abstract description 12
- 230000000711 cancerogenic effect Effects 0.000 abstract description 4
- 231100000315 carcinogenic Toxicity 0.000 abstract description 4
- 239000012855 volatile organic compound Substances 0.000 abstract description 4
- 239000011248 coating agent Substances 0.000 description 44
- 238000000576 coating method Methods 0.000 description 44
- 229910004298 SiO 2 Inorganic materials 0.000 description 42
- 238000005260 corrosion Methods 0.000 description 22
- 238000012360 testing method Methods 0.000 description 19
- 230000007797 corrosion Effects 0.000 description 15
- 239000004593 Epoxy Substances 0.000 description 11
- 230000000694 effects Effects 0.000 description 9
- 239000002184 metal Substances 0.000 description 9
- 229910052751 metal Inorganic materials 0.000 description 9
- 238000004626 scanning electron microscopy Methods 0.000 description 8
- 238000002156 mixing Methods 0.000 description 7
- 239000000243 solution Substances 0.000 description 7
- 239000000203 mixture Substances 0.000 description 6
- 239000002245 particle Substances 0.000 description 6
- 229920005989 resin Polymers 0.000 description 6
- 239000011347 resin Substances 0.000 description 6
- 238000001878 scanning electron micrograph Methods 0.000 description 6
- 238000001228 spectrum Methods 0.000 description 6
- 239000006087 Silane Coupling Agent Substances 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 239000012299 nitrogen atmosphere Substances 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- 125000003700 epoxy group Chemical group 0.000 description 4
- 239000011148 porous material Substances 0.000 description 4
- 150000003839 salts Chemical class 0.000 description 4
- 239000007921 spray Substances 0.000 description 4
- 238000005536 corrosion prevention Methods 0.000 description 3
- 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 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Chemical compound [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 description 3
- 230000005476 size effect Effects 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 241000282414 Homo sapiens Species 0.000 description 2
- 238000005481 NMR spectroscopy Methods 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 229910000831 Steel Inorganic materials 0.000 description 2
- 238000005054 agglomeration Methods 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 229920006334 epoxy coating Polymers 0.000 description 2
- 239000000945 filler Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 239000007769 metal material Substances 0.000 description 2
- 239000002086 nanomaterial Substances 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 239000010959 steel Substances 0.000 description 2
- 229930185605 Bisphenol Natural products 0.000 description 1
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 1
- CTKINSOISVBQLD-UHFFFAOYSA-N Glycidol Chemical compound OCC1CO1 CTKINSOISVBQLD-UHFFFAOYSA-N 0.000 description 1
- 244000137852 Petrea volubilis Species 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 1
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 1
- 238000006482 condensation reaction Methods 0.000 description 1
- 229920001940 conductive polymer Polymers 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- ZOMNIUBKTOKEHS-UHFFFAOYSA-L dimercury dichloride Chemical class Cl[Hg][Hg]Cl ZOMNIUBKTOKEHS-UHFFFAOYSA-L 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000010292 electrical insulation Methods 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000001815 facial effect Effects 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 238000003682 fluorination reaction Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000001453 impedance spectrum Methods 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 238000005191 phase separation Methods 0.000 description 1
- 238000005498 polishing Methods 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000007142 ring opening reaction Methods 0.000 description 1
- 238000007790 scraping Methods 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 230000003075 superhydrophobic effect Effects 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D163/00—Coating compositions based on epoxy resins; Coating compositions based on derivatives of epoxy resins
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/08—Anti-corrosive paints
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/20—Diluents or solvents
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/60—Additives non-macromolecular
- C09D7/61—Additives non-macromolecular inorganic
- C09D7/62—Additives non-macromolecular inorganic modified by treatment with other compounds
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/70—Additives characterised by shape, e.g. fibres, flakes or microspheres
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
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- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
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- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Paints Or Removers (AREA)
Abstract
The invention provides a fluorinated silica/water-based epoxy resin composite anticorrosive paint and a preparation method thereof, wherein hydrophilic nano silica and 3- (methacryloyloxy) propyl trimethoxy silane are refluxed in an anaerobic environment at 70-80 ℃, products are washed and dried, the obtained double-bonded hydrophilic nano silica nano microsphere and hexafluorobutyl acrylate are polymerized in the anaerobic environment, the products are washed and dried, and the obtained FSiO is obtained 2 The nanometer microsphere is uniformly dispersed in the aqueous epoxy resin, the nanometer microsphere accounts for 0.1-0.9% of the total mass of the epoxy resin and the curing agent in the aqueous epoxy resin, and then the fluorinated silica/aqueous epoxy resin composite anticorrosive paint is obtained by filtering. The invention solves the problem that the traditional solvent-based anticorrosive paint contains a large amount of carcinogenic volatile organic compounds, is green and environment-friendly, and has excellent mechanical property and long-acting anticorrosive capability.
Description
Technical Field
The invention belongs to the field of preparation of anti-corrosion paint, and relates to fluorinated silica/water-based epoxy resin composite anti-corrosion paint and a preparation method thereof.
Background
For a long time, the metal material is an important material applied to building, aviation navigation, conveying pipelines and bridge construction, and plays an indispensable important role in daily life of people. However, the metal is very easy to react with the oxidizing substances in the air and is corroded by the oxidizing substances, so that the metal loses excellent mechanical properties, and even the life safety of human beings is endangered in serious cases. Therefore, corrosion protection of metals has become a problem to be solved. Among various metal corrosion prevention technologies, paint protection is the simplest and most effective method.
Currently, cathodic and anodic protection and coating protection are the three most dominant protection measures. Wherein, directly coating an organic coating on the surface of a metal material is based on the principle of isolating corrosive medium, and is the simplest solution with lower cost at present. Epoxy resins are generic names of a class of high molecular polymers containing two or more epoxy groups in the molecule, and have the formula (C 11 H 12 O 3 ) n . The epoxy group in the molecular structure can be positioned at any position in the molecular skeleton, is generally distributed at two ends of the chain, forms a ring structure by two carbons and one oxygen, and is a common organic coating material. Contains a large number of active and polar groups, can be crosslinked and cured with different curing agents, wherein epoxy groups can undergo ring-opening reaction, secondary hydroxyl groups can undergo condensation reaction, so that different properties can be generated with different additives, and the epoxy resin can be widely used for metal corrosion prevention, and has stable size, good mechanical properties, higher electrical insulation property and extremely strong tolerance after curing. The designability and the pluripotency of the structure of the composite material lead the composite material taking the epoxy resin as a matrix to be widely applied. At the same time, the epoxy resin has strong adhesive force and canThe coating is applied at normal temperature, has excellent manufacturability, is simple and convenient to operate, and is suitable for being used as a coating. The most used types in industry are bisphenol based ether epoxy resins in glycidol.
In corrosion prevention, the epoxy resin coating mainly coats the surface of metal which is easy to corrode, and isolates the contact of the metal with corrosion factors in the air. Epoxy resins have very wide application in the coating field. But at the same time has some disadvantages: two epoxy groups in the epoxy molecule can generate a net structure after being cured by a curing agent, so that the coating becomes a surface and can generate certain brittleness; after the start of curing, the solvent inside the resin is released, and a plurality of microcracks are generated on the surface of the coating, and the microcracks provide a passage for corrosive media to reach the metal surface, thereby greatly reducing the corrosion resistance of the coating.
In order to further improve the anti-corrosion capability of the epoxy resin, inorganic nano particles, conductive polymers, super-hydrophobic materials, corrosion inhibitors or design new epoxy resin structures and the like can be added to improve the anti-corrosion function of the epoxy resin. The nano material refers to fine particles with the particle size of more than 1nm and less than 100 nm. Compared with the common powder, the nano material has surface effect, small-size effect and quantum size effect. The surface effect, also called interface effect, generally refers to the effect of the ratio of the number of atoms on the surface of the nanoparticle to the total number of atoms on the surface of the nanoparticle on the characteristics of the substance, and when the size of the nanoparticle is reduced, the number of atoms on the surface of the nanoparticle is increased, the specific surface area and the surface energy of the nanoparticle are also increased, and the nanoparticle shows high chemical activity, and is specifically shown in table 1.
TABLE 1 relationship between nanoparticle size and surface atom ratio
The small size effect is also known as the volumetric effect. When the particle volume of the nanoparticle is reduced, the specific surface area of the particle is significantly increased, so that the nanoparticle has characteristics which are not possessed by the prior art. The quantum size effect refers to a phenomenon in which when the particle diameter of a particle is small to some extent, the electron energy level around the metal fermi level is changed from a general continuous energy level to a split energy level.
Nano SiO 2 Has larger specific surface area, higher surface activity and poorer stability, and the performances lead to the nano SiO 2 Are easy to agglomerate with each other, so that the epoxy resin can not be well combined with the epoxy resin, and even if hydrophilic nano SiO is selected 2 Because of the hydrophilicity and oleophobicity, the epoxy resin is not easy to uniformly disperse in an organic medium to cause the two-phase separation of a system, and the improvement of the anticorrosion capacity of the epoxy resin cannot be realized.
Disclosure of Invention
Aiming at the problems existing in the prior art, the invention provides the fluorinated silica/water-based epoxy resin composite anticorrosive paint and the preparation method thereof, which not only solve the problem that the traditional solvent-based anticorrosive paint contains a large amount of carcinogenic volatile organic compounds, but also have the advantages of environmental protection, excellent mechanical property and long-acting anticorrosive capability.
In order to achieve the above purpose, the invention is realized by adopting the following technical scheme:
the preparation method of the fluorinated silica/water-based epoxy resin composite anticorrosive paint comprises the following steps:
Preferably, the hydrophilic nano-silica and 3- (methacryloyloxy) propyl trimethoxysilane in step 1 are subjected to reflux reaction in toluene, the mass of toluene being 20 times that of the hydrophilic nano-silica.
Preferably, in the step 1, hydrophilic nano silicon dioxide is firstly added into toluene for ultrasonic treatment for 25-35min, then stirred for 15-25min under the protection of nitrogen, and finally 3- (methacryloyloxy) propyl trimethoxy silane is added for reflux reaction under continuous stirring.
Preferably, the reflux reaction described in step 1 is carried out for 20-24 hours.
Preferably, the nanoparticle, hexafluorobutyl acrylate and initiator in the step 2 are subjected to polymerization reaction in toluene, wherein the initiator is azodiisobutyronitrile, the ratio of the hexafluorobutyl acrylate to the toluene is (2.5-3.5) g (18-22) mL, and the azodiisobutyronitrile accounts for 1-2% of the total mass of the nanoparticle and the hexafluorobutyl acrylate.
Preferably, the polymerization reaction described in step 2 is carried out at 75-85℃for 22-26h.
Preferably, the products of step 1 and step 2 are washed with toluene and dried at 55-65℃for 20-24 hours.
Preferably, step 3 comprises adding FSiO to the epoxy resin 2 Stirring uniformly after nano-microspheres, sequentially adding a curing agent, a defoaming agent, a leveling agent and a substrate wetting agent under the stirring condition, and finally filtering by using filter cloth to obtain the fluorinated silica/water-based epoxy resin composite anticorrosive paint.
Further, the mass ratio of the epoxy resin to the curing agent to the defoaming agent to the leveling agent to the substrate wetting agent is 30 (8-12) (0.4-0.6), the defoaming agent is 902W, the leveling agent is BYK333, and the substrate wetting agent is 4100.
The fluorinated silica/water-based epoxy resin composite anticorrosive paint obtained by the preparation method of any one of the fluorinated silica/water-based epoxy resin composite anticorrosive paint.
Compared with the prior art, the invention has the following beneficial effects:
the invention relates to a preparation method of fluorinated silica/water-based epoxy resin composite anticorrosive paint, which is characterized in that hydrophilic nano silica and silane coupling agent 3- (methacryloyloxy) propyl trimethoxy silane are polymerized in a reflux reaction to obtain double-bonded SiO 2 Which can be further polymerized with hexafluorobutyl acrylate to give modified fluorinated silica FSiO 2 Filler capable of being directly used for water-based epoxy resin coating and FSiO 2 The composite coating is prepared by dispersing the composite coating into the water-based epoxy resin, and compared with the water-based epoxy resin coating, the impedance of the formed coating is improved by 2 orders of magnitude, and the corrosion resistance and the mechanical property are obviously improved. The invention selects fluorinated silica nano particles to fill microcracks generated by epoxy resin curing, and the inorganic nano particles have larger specific surface area and higher surface energy, so that a small amount of the inorganic nano particles can be added to achieve remarkable performance improvement, and the problem that the microcracks, pore channels and the like generated by the pure epoxy resin coating in use affect the corrosion resistance is effectively solved. The invention carries out surface modification on hydrophilic nano silicon dioxide by silane coupling agent 3- (methacryloyloxy) propyl trimethoxy silane (KH 570) and hexafluorobutyl acrylate (HFBA), and carries out surface modification on modified fluorinated silicon dioxide (FSiO) 2 ) The particles are dispersed into the water-based epoxy resin, and the prepared fluorinated nano silicon dioxide/epoxy resin composite anticorrosive paint blocks microcracks and pore canals generated by the paint, so that the anticorrosive performance of the paint is improved.
The traditional solvent-based anticorrosive paint contains a large amount of carcinogenic volatile organic compounds, causes great harm to human bodies and the environment, and has poor mechanical property and long-acting anticorrosive property of the pure water-based epoxy resin coating. FSiO prepared by the invention 2 Compared with the traditional solvent-based paint, the water-based epoxy resin composite anticorrosive paint solves the problem that the traditional solvent-based anticorrosive paint contains a large amount of carcinogenic volatile organic compounds, is green and environment-friendly, and has excellent mechanical property and long-acting anticorrosive property. FSiO obtained by the invention 2 The coating formed by the aqueous epoxy resin composite coating has good corrosion resistance and mechanical propertyGreatly improves the electrochemical impedance by 2 orders of magnitude.
Drawings
FIG. 1a is SiO 2 The composite roadmap for KH 570.
FIG. 1b is FSiO 2 Is a composite roadmap of (a).
FIG. 2a is SiO 2 、SiO 2 @KH570、FSiO 2 FTIR test (by fourier infrared spectrometer).
FIG. 2b is SiO 2 、SiO 2 @KH570、FSiO 2 A kind of electronic device 1 H NMR test pattern (by 600MHz nuclear magnetic resonance spectrometer).
FIG. 3 is SiO 2 @KH570、FSiO 2 TGA test pattern of (c).
FIG. 4a is SiO 2 EDS energy spectrum of KH570 (tested by scanning electron microscopy).
FIG. 4b is SiO 2 EDS energy spectrum of KH570 (tested by scanning electron microscopy).
FIG. 4c is SiO 2 EDS energy spectrum of KH570 (tested by scanning electron microscopy).
FIG. 4d is FSiO 2 Is measured by scanning electron microscopy.
FIG. 4e is FSiO 2 Is measured by scanning electron microscopy.
FIG. 4f is FSiO 2 Is measured by scanning electron microscopy.
FIG. 5 is a pure water epoxy coating, FSiO 2 Drawing test chart of water-based epoxy resin composite anti-corrosion coating (tested by a servo material multifunctional high-low temperature control tester).
FIG. 6a is a cross-sectional SEM image (by scanning electron microscope test) of a pure water type epoxy resin coating.
FIG. 6b is FSiO 2 SEM image of the cross-section of the 1/aqueous epoxy composite corrosion protection coating (by scanning electron microscope test).
FIG. 6c is FSiO 2 -SEM image of the cross-section of the 2/aqueous epoxy composite corrosion protection coating (by scanning electron microscopy).
FIG. 6d is FSiO 2 -SEM image of cross-section of 3/aqueous epoxy composite corrosion protection coating (by scanning electron microscope test).
FIG. 6e is FSiO 2 -SEM image of the cross-section of the 4/aqueous epoxy composite corrosion protection coating (by scanning electron microscopy).
FIG. 6f is FSiO 2 -SEM image of cross-section of 5/aqueous epoxy composite corrosion protection coating (by scanning electron microscope test).
FIG. 7a is a pure water epoxy coating, FSiO 2 Aqueous epoxy composite corrosion resistant coating electrochemical impedance test pattern (through electrochemical workstation test).
Fig. 7b is an enlarged view of the inside of the rectangular frame in fig. 7 a.
FIG. 8a is FSiO 2 Salt spray test electrochemical impedance plot of the 1/waterborne epoxy composite corrosion resistant coating (by electrochemical workstation test).
Fig. 8b is an enlarged view of the inside of the rectangular frame in fig. 8 a.
Detailed Description
In order that those skilled in the art will better understand the solution of the present invention, a technical solution of an embodiment of the present invention will be clearly and completely described below with reference to the accompanying drawings in the embodiment of the present invention, and it is apparent that the described embodiment is only a part of the embodiment of the present invention, not all the embodiments.
Fluorinated Silica (FSiO) of the present invention 2 ) The preparation method of the water-based epoxy resin composite anticorrosive paint comprises the following steps:
As shown in FIG. 1a, the hydrophilic nanosilica was double-bonded to give fluorinated silica (SiO 2 @kh570) nanoparticles, i.e. 80mL of toluene was charged into a reaction flask, in which hydrophilic silica (3.488 g) accounting for 5.0% of the mass of toluene was ultrasonically dispersed for 25-35min, then stirred under nitrogen for 15-25min, and 2.5-3g of 3- (methacryloyloxy) propyltrimethoxysilane (silane coupling agent KH 570) was added. The obtained mixture is continuously stirred and refluxed for 20-24h at 70-80 ℃, and the silane coupling agent (KH 570) is hydrophilicThe silicon oxide is modified, and double bonding of the nano silicon dioxide is completed through grafting. Filtration of the grafted SiO 2 And washing with toluene to remove excessive KH570, and drying in vacuum oven at 55-65deg.C for 20-24 hr to obtain SiO 2 @ KH570 nanoparticle.
As shown in FIG. 1b, siO is deposited 2 Copolymerization of KH570 with hexafluorobutyl acrylate (HFBA) gives Fluorinated Silica (FSiO) 2 ) A nanoparticle; siO to be dried 2 0.2-0.4g of KH570 nano-microsphere and 2.5-3.5g of hexafluorobutyl acrylate (HFBA) are added into a reaction flask, and SiO is added 2 1-2% of initiator Azobisisobutyronitrile (AIBN) with the total mass of KH570 nano-microsphere and hexafluorobutyl acrylate, and 18-22mL of solvent toluene are added. Introducing N 2 Protected and stirred under nitrogen for 25-35min, after which the product was filtered and washed with a large amount of toluene after polymerization at 75-85 ℃ for 22-26h. Finally, the obtained polymer is dried in a vacuum oven at 55-65 ℃ for 20-24 hours to obtain FSiO 2 A nanometer microsphere.
FSiO of different masses was slowly added to 5 parts of epoxy resin 30g, respectively 2 The nanometer microsphere is stirred for 30-45 min by a mechanical dispersion method by using a dispersing machine, the adding amount is 0.1-0.9 percent of the mass of the epoxy resin and the curing agent F0750 respectively (specifically, 0.04g, 0.12g, 0.20g, 0.28g and 0.36g are sequentially added), then, the curing agent F0750-12 g is respectively added, stirring is carried out for 3-5min at 600-800r/min, uniformly mixing is carried out, 0.4-0.6g of defoaming agent 902W,0.4-0.6g of flatting agent BYK333 and 0.4-0.6g of base material wetting agent 4100 are respectively added at intervals under the same stirring speed, and the interval time is 3-5min. Finally filtering with 200-mesh filter cloth to obtain FSiO 2 Aqueous epoxy resin composite anticorrosive paint.
Polishing Q235 steel plate with 60mm×130mm and 0.5mm thickness with 400mm sand paper, drying with ethanol, naturally drying at room temperature, and collecting FSiO 2 The aqueous epoxy resin composite anticorrosive paint is coated on the treated steel plate by a 150 mu m magnetic rod in a scraping way, and is dried in a baking oven, then is sealed by wax, and finally is fedElectrochemical impedance and salt spray testing were performed.
The coating samples were subjected to corrosion testing using an electrochemical workstation. The counter electrode used for the test was 1cm 2 The reference electrode is a saturated calomel electrode, and the sample working electrode is exposed for 1cm 2 The periphery is insulated by wax sealing, and an aqueous solution of NaCl with the mass fraction of 3.5wt% is used as electrolyte, and a three-electrode system is constructed in an electromagnetic shielding box for electrochemical impedance test. Electrochemical impedance spectrum is tested under the condition of stable open circuit voltage, and the test frequency is 10 -2 -10 5 Hz,20mV sinusoidal voltage. Three parallel samples were used for each sample during the test to reduce errors.
Example 1
Preparation of FSiO by the invention 2 The specific steps of the water-based epoxy resin composite anticorrosive paint are as follows:
(1)SiO 2 preparation of @ KH570 nano-microsphere
The reaction flask was charged with 80mL of toluene, and hydrophilic silica accounting for 5.0% of the mass of toluene was ultrasonically dispersed therein for 30min. Then stirred under nitrogen for 20min, 2.5g (2.39 mL) of 3- (methacryloyloxy) propyltrimethoxysilane (KH 570) was added. The resulting mixture was continuously stirred at 75℃under reflux for 24h. Filtration of the grafted SiO 2 And washed thoroughly with toluene to remove excess KH570, and dried in a vacuum oven at 60deg.C for 24h to give SiO 2 @ KH570 nanoparticle.
(2)FSiO 2 Preparation of nano-microsphere
To dry SiO 2 0.3g of KH570 nano-microsphere and 3g of hexafluorobutyl acrylate (HFBA) were added to the reaction flask, 66.0mg (2 wt%) of Azobisisobutyronitrile (AIBN) as an initiator was added, and 20mL of toluene was added as a solvent. Introducing N 2 Protected and stirred for 30min under nitrogen atmosphere, after polymerization for 24h at 80 ℃, the product was filtered and washed with a large amount of toluene. Finally, grafted SiO 2 Drying in a vacuum oven at 60deg.C for 24h to obtain FSiO 2 A nanometer microsphere.
(3)FSiO 2 Preparation of aqueous epoxy resin composite anticorrosive paint
0.1wt% (0.04 g) FSiO was slowly added to 30g of epoxy resin 2 Stirring the nano microspheres for 35min, adding the curing agent F0750 10g, stirring at 800r/min for 5min, uniformly mixing, and sequentially adding 0.5g 902W,0.5g BYK333,0.5g4100 at intervals for 5min at the same stirring rate. Finally filtering with 200-mesh filter cloth to obtain FSiO 2 Aqueous epoxy resin composite anticorrosive paint, which is marked as FSiO 2 -1/WEP。
Example 2
Preparation of FSiO by the invention 2 The specific steps of the water-based epoxy resin composite anticorrosive paint are as follows:
(1)SiO 2 preparation of @ KH570 nano-microsphere
The reaction flask was charged with 80mL of toluene, and hydrophilic silica accounting for 5.0% of the mass of toluene was ultrasonically dispersed therein for 30min. Then stirred under nitrogen for 20min, 2.5g (2.39 mL) of 3- (methacryloyloxy) propyltrimethoxysilane (KH 570) was added. The resulting mixture was continuously stirred at 75℃under reflux for 24h. Filtration of the grafted SiO 2 And washed thoroughly with toluene to remove excess KH570, and dried in a vacuum oven at 60deg.C for 24h to give SiO 2 @ KH570 nanoparticle.
(2)FSiO 2 Preparation of nano-microsphere
To dry SiO 2 0.3g of KH570 nano-microsphere and 3g of hexafluorobutyl acrylate (HFBA) were added to the reaction flask, 66.0mg (2 wt%) of Azobisisobutyronitrile (AIBN) as an initiator was added, and 20mL of toluene was added as a solvent. Introducing N 2 Protected and stirred for 30min under nitrogen atmosphere, after polymerization for 24h at 80 ℃, the product was filtered and washed with a large amount of toluene. Finally, grafted SiO 2 Drying in a vacuum oven at 60deg.C for 24h to obtain FSiO 2 A nanometer microsphere.
(3)FSiO 2 Preparation of aqueous epoxy resin composite anticorrosive paint
0.3wt% (0.12 g) FSiO was slowly added to 30g of epoxy resin 2 Stirring the nanometer microsphere for 40min, adding the curing agent F0750 10g, stirring at 800r/min for 5min, mixing, sequentially adding 0.4g 902W,0.5g BYK333,0.5g4100 at intervals under the same stirring rate for 5min. Finally filtering with 200-mesh filter cloth to obtain FSiO 2 Aqueous epoxy resin composite anticorrosive paint, which is marked as FSiO 2 -2/WEP。
Example 3
Preparation of FSiO by the invention 2 The specific steps of the water-based epoxy resin composite anticorrosive paint are as follows:
(1)SiO 2 preparation of @ KH570 nano-microsphere
A reaction flask was charged with 80mL of toluene, and hydrophilic silica accounting for 5.0% of the mass of toluene was ultrasonically dispersed therein for 30
And (5) min. Then stirred under nitrogen for 20min, 2.5g (2.39 mL) of 3- (methacryloyloxy) propyltrimethoxysilane (KH 570) was added. The resulting mixture was continuously stirred at 75℃under reflux for 24h. Filtration of the grafted SiO 2 And washed thoroughly with toluene to remove excess KH570, and dried in a vacuum oven at 60deg.C for 24h to give SiO 2 @ KH570 nanoparticle.
(2)FSiO 2 Preparation of nano-microsphere
To dry SiO 2 0.3g of KH570 nano-microsphere and 3g of hexafluorobutyl acrylate (HFBA) were added to the reaction flask, 66.0mg (2 wt%) of Azobisisobutyronitrile (AIBN) as an initiator was added, and 20mL of toluene was added as a solvent. Introducing N 2 Protected and stirred for 30min under nitrogen atmosphere, after polymerization for 24h at 80 ℃, the product was filtered and washed with a large amount of toluene. Finally, grafted SiO 2 Drying in a vacuum oven at 60deg.C for 24h to obtain FSiO 2 A nanometer microsphere.
(3)FSiO 2 Preparation of aqueous epoxy resin composite anticorrosive paint
0.5wt% (0.20 g) FSiO was slowly added to 30g of epoxy resin 2 Stirring the nano microspheres for 45min, adding the curing agent F0750 10g, stirring at 800r/min for 5min, uniformly mixing, and sequentially adding 0.5g 902W,0.4g BYK333,0.5g4100 at intervals for 5min at the same stirring rate. Finally filtering with 200-mesh filter cloth to obtain FSiO 2 Aqueous epoxy resin composite anticorrosive paint, which is marked as FSiO 2 -3/WEP。
Example 4
The invention is adoptedPreparation of FSiO 2 The specific steps of the water-based epoxy resin composite anticorrosive paint are as follows:
(1)SiO 2 preparation of @ KH570 nano-microsphere
The reaction flask was charged with 80mL of toluene, and hydrophilic silica accounting for 5.0% of the mass of toluene was ultrasonically dispersed therein for 30min. Then stirred under nitrogen for 20min, 2.5g (2.39 mL) of 3- (methacryloyloxy) propyltrimethoxysilane (KH 570) was added. The resulting mixture was continuously stirred at 75℃under reflux for 24h. Filtration of the grafted SiO 2 And washed thoroughly with toluene to remove excess KH570, and dried in a vacuum oven at 60deg.C for 24h to give SiO 2 @ KH570 nanoparticle.
(2)FSiO 2 Preparation of nano-microsphere
To dry SiO 2 0.3g of KH570 nano-microsphere and 3g of hexafluorobutyl acrylate (HFBA) were added to the reaction flask, 66.0mg (2 wt%) of Azobisisobutyronitrile (AIBN) as an initiator was added, and 20mL of toluene was added as a solvent. Introducing N 2 Protected and stirred for 30min under nitrogen atmosphere, after polymerization for 24h at 80 ℃, the product was filtered and washed with a large amount of toluene. Finally, grafted SiO 2 Drying in a vacuum oven at 60deg.C for 24h to obtain FSiO 2 A nanometer microsphere.
(3)FSiO 2 Preparation of aqueous epoxy resin composite anticorrosive paint
0.7wt% (0.28 g) FSiO was slowly added to 30g of epoxy resin 2 Stirring the nano microspheres for 45min, adding the curing agent F0750 10g, stirring at 800r/min for 5min, uniformly mixing, and sequentially adding 0.5g 902W,0.5g BYK333,0.4g4100 at intervals for 5min at the same stirring rate. Finally filtering with 200-mesh filter cloth to obtain FSiO 2 Aqueous epoxy resin composite anticorrosive paint, which is marked as FSiO 2 -4/WEP。
Example 5
Preparation of FSiO by the invention 2 The specific steps of the water-based epoxy resin composite anticorrosive paint are as follows:
(1)SiO 2 preparation of @ KH570 nano-microsphere
Into a reaction flask was charged 80mL of toluene, which was 5.0 mass% based on toluene% of hydrophilic silica was ultrasonically dispersed therein for 30min. Then stirred under nitrogen for 20min, 2.5g (2.39 mL) of 3- (methacryloyloxy) propyltrimethoxysilane (KH 570) was added. The resulting mixture was continuously stirred at 75℃under reflux for 24h. Filtration of the grafted SiO 2 And washed thoroughly with toluene to remove excess KH570, and dried in a vacuum oven at 60deg.C for 24h to give SiO 2 @ KH570 nanoparticle.
(2)FSiO 2 Preparation of nano-microsphere
To dry SiO 2 0.3g of KH570 nano-microsphere and 3g of hexafluorobutyl acrylate (HFBA) were added to the reaction flask, 66.0mg (2 wt%) of Azobisisobutyronitrile (AIBN) as an initiator was added, and 20mL of toluene was added as a solvent. Introducing N 2 Protected and stirred for 30min under nitrogen atmosphere, after polymerization for 24h at 80 ℃, the product was filtered and washed with a large amount of toluene. Finally, grafted SiO 2 Drying in a vacuum oven at 60deg.C for 24h to obtain FSiO 2 A nanometer microsphere.
(3)FSiO 2 Preparation of aqueous epoxy resin composite anticorrosive paint
0.9wt% (0.36 g) FSiO was slowly added to 30g of epoxy resin 2 Stirring the nano microspheres for 45min, adding the curing agent F0750 10g, stirring at 800r/min for 5min, uniformly mixing, and sequentially adding 0.4g 902W,0.4g BYK333,0.4g4100 at intervals for 5min at the same stirring rate. Finally filtering with 200-mesh filter cloth to obtain FSiO 2 Aqueous epoxy resin composite anticorrosive paint, which is marked as FSiO 2 -5/WEP。
In FIG. 2a, a peak of carbon-carbon double bond appears at 1710, indicating successful grafting of silane coupling agent KH570 onto nanosilica, a peak of fluorocarbon bond at 1290, a peak of carbon-oxygen-carbon bond at 1750, indicating successful grafting of hexafluorobutyl acrylate onto silica, fluorinated silica FSiO 2 The preparation is successful. In FIG. 2b, a double bond peak appears at about 6ppm chemical shift after double bonding, indicating successful grafting, and the double bond disappears after fluorination, indicating fluorinated silica FSiO 2 The preparation is successful.
As shown in FIG. 3, siO obtained after KH570 modification 2 Heating to @ KH570There was also 89.30wt% residue at 700 ℃. FSiO 2 The mass fraction of the residue during heating of the sample to 700℃at room temperature was 37.29% by weight, indicating that 52.01% by weight of HFBA was polymerized to SiO 2 On KH 570.
FIGS. 4a to f are SiO obtained by facial scanning 2 @KH570 and FSiO 2 Is an EDS energy spectrum and a related data graph. FIG. 4a, FIG. 4b, FIG. 4c is SiO 2 EDS energy spectrum at KH570 and related data, from which the content of F element is 1%; FIG. 4d, FIG. 4e, FIG. 4f is FSiO 2 Is an EDS energy spectrum and a related data graph. From these figures, the content of F element was found to be 17%. Indicating successful preparation of fluorinated silica.
As shown in fig. 5, the stress strain of the aqueous epoxy resin WEP was 8.22KPa and 14.84%, respectively. The aqueous epoxy resin is obtained according to the following process: adding a curing agent F0750 10g into 30g of epoxy resin, stirring for 5min at 800r/min, uniformly mixing, sequentially adding 0.3-0.5g 902W,0.5g BYK333,0.5g4100 at intervals of 5min, and finally filtering with 200-mesh filter cloth to obtain the water-based epoxy resin. As can be seen, with FSiO 2 The addition amount of the nano particles is increased, the stress of the paint film is gradually reduced, and the strain is increased and then reduced. At an addition of 0.5wt%, the strain reached a maximum of 93.15%. Due to FSiO 2 The addition of the nano particles fills the inherent defects of the epoxy resin paint film, improves the continuity of the resin and enhances the strain of the resin. With FSiO 2 The amount of nanoparticles added is continuously increased, and the strain is decreased. This is due to FSiO 2 The agglomeration of the nano particles causes that the specific surface area is the largest when the nano particles are dispersed, the bonding of a contact interface is firmer, and when the resin is deformed, larger stress yield is generated, larger energy can be absorbed, and the resin has good toughening effect macroscopically. And the agglomeration phenomenon can be generated when the excessive nano particles are added, the specific surface area is reduced, and defects are formed in the numerical value more easily, so that the mechanical property of the resin is reduced.
FIG. 6b, FIG. 6c, FIG. 6d, FIG. 6e, FIG. 6f shows FSiO obtained in the above 5 examples 2 As can be seen from the SEM cross-sectional view of the aqueous epoxy composite anticorrosive coating in figure 6a,WEP appears to be evident as a distinct brittle fracture, with a break-out of flatness, and some distinct microscopic voids. With FSiO 2 Increased amounts of nanoparticles added, FSiO 2 The cross section of the epoxy resin composite coating becomes an obvious embedded lamellar relative to WEP, and the cross section becomes smoother. At FSiO 2 When the addition amount of the nano particles is 0.1wt%, the lamellar fracture structure of the section is obviously more than other samples, the micro-pores are fewer, which indicates that the paint film is more compact, and 0.1wt% of FSiO 2 The addition of the nano particles effectively solves the problems of microcracks and pore canals generated in the curing process of the waterborne epoxy resin coating. With FSiO 2 The addition of nanoparticles, between 0.3 and 0.9wt% of the composite paint film also appears as embedded lamellar, but relative to FSiO 2 Less 1/epoxy composite coating and holes on the surface of the cross section relative to FSiO 2 The 1/epoxy resin composite coating is more, and the surface is agglomerated.
As can be seen from fig. 7a, 7b, FSiO 2 The electrochemical impedance modulus of the-1/WEP composite coating is maximally 1.171 multiplied by 10 8 Ω·cm 2 ，FSiO 2 The electrochemical impedance modulus of the-2/WEP composite coating is 8.748 multiplied by 10 7 Ω·cm 2 ，FSiO 2 The electrochemical impedance modulus of the-3/WEP composite coating is 5.647 multiplied by 10 7 Ω·cm 2 ，FSiO 2 The electrochemical impedance modulus of the-3/WEP composite coating is 2.758 multiplied by 10 7 Ω·cm 2 ，FSiO 2 -5/WEP composite coating having an electrochemical impedance modulus of 3.327×10 7 Ω·cm 2 Electrochemical impedance modulus of the WEP coating is 10 7 Ω·cm 2 Left and right, with filler FSiO 2 Nanoparticle addition, FSiO 2 The electrochemical impedance modulus of the/WEP composite coating gradually decreases.
As can be seen from FIG. 8a and FIG. 8b, at 0h FSiO 2 Electrochemical impedance moduli of-1/WEP of 1.171×10 respectively 8 Ω·cm 2 The electrochemical impedance modulus gradually decreases with increasing salt spray time, and FSiO after 480h salt spray test is carried out 2 Electrochemical impedance moduli of-1/WEP were reduced to 8.765X 10, respectively 6 Ω·cm 2 。
To sum up, FSiO 2 Compared with the pure epoxy resin coating, the water-based epoxy resin composite anti-corrosion coating has the advantages of increased strain, increased electrochemical impedance and obviously improved mechanical property and anti-corrosion property.
Claims (10)
1. The preparation method of the fluorinated silica/water-based epoxy resin composite anticorrosive paint is characterized by comprising the following steps:
step 1, carrying out reflux reaction on hydrophilic nano silicon dioxide and 3- (methacryloyloxy) propyl trimethoxysilane according to the mass ratio of 3.488 (2.5-3) in an anaerobic environment at 70-80 ℃ to obtain a reaction solution a, washing and drying a product in the reaction solution a to obtain double-bonded hydrophilic nano silicon dioxide nano microspheres;
step 2, carrying out polymerization reaction on double-bonded hydrophilic nano silicon dioxide nano microspheres and hexafluorobutyl acrylate in an oxygen-free environment under the action of an initiator, wherein the mass ratio of the nano microspheres to the hexafluorobutyl acrylate is (0.2-0.4): 2.5-3.5 to obtain a reaction solution b, washing and drying a product in the reaction solution b to obtain FSiO 2 A nanoparticle;
step 3, FSiO 2 The nano-microspheres are uniformly dispersed in the aqueous epoxy resin, the nano-microspheres account for 0.1-0.9% of the total mass of the epoxy resin and the curing agent in the aqueous epoxy resin, and then the fluorinated silica/aqueous epoxy resin composite anticorrosive paint is obtained after filtration.
2. The method for preparing the fluorinated silica/water-based epoxy resin composite anticorrosive paint according to claim 1, wherein in the step 1, the hydrophilic nano silica and 3- (methacryloyloxy) propyl trimethoxy silane are subjected to reflux reaction in toluene, and the mass of toluene is 20 times that of the hydrophilic nano silica.
3. The preparation method of the fluorinated silica/water-based epoxy resin composite anticorrosive paint according to claim 2, wherein in the step 1, hydrophilic nano silica is firstly added into toluene for ultrasonic treatment for 25-35min, then stirred for 15-25min under the protection of nitrogen, and finally 3- (methacryloyloxy) propyl trimethoxysilane is added for reflux reaction under continuous stirring.
4. The method for preparing the fluorinated silica/aqueous epoxy resin composite anticorrosive paint according to claim 1, wherein the reflux reaction in the step 1 is carried out for 20-24 hours.
5. The preparation method of the fluorinated silica/water-based epoxy resin composite anticorrosive paint according to claim 1, wherein in the step 2, the nano-microsphere, hexafluorobutyl acrylate and an initiator are subjected to polymerization reaction in toluene, the initiator is azobisisobutyronitrile, the ratio of hexafluorobutyl acrylate to toluene is (2.5-3.5) g (18-22) mL, and azobisisobutyronitrile accounts for 1% -2% of the total mass of the nano-microsphere and hexafluorobutyl acrylate.
6. The method for preparing the fluorinated silica/water-based epoxy resin composite anticorrosive paint according to claim 1, wherein the polymerization reaction in the step 2 is carried out at 75-85 ℃ for 22-26 hours.
7. The method for preparing the fluorinated silica/water-based epoxy resin composite anticorrosive paint according to claim 1, wherein the products in the step 1 and the step 2 are washed by toluene, and the drying is carried out at 55-65 ℃ for 20-24 hours.
8. The method for preparing the fluorinated silica/water-based epoxy resin composite anticorrosive paint according to claim 1, wherein step 3 comprises the steps of adding FSiO into the epoxy resin 2 Stirring uniformly after nano-microspheres, sequentially adding a curing agent, a defoaming agent, a leveling agent and a substrate wetting agent under the stirring condition, and finally filtering by using filter cloth to obtain the fluorinated silica/water-based epoxy resin composite anticorrosive paint.
9. The preparation method of the fluorinated silica/water-based epoxy resin composite anticorrosive paint according to claim 8, wherein the mass ratio of the epoxy resin to the curing agent to the defoamer to the leveling agent to the substrate wetting agent is 30 (8-12) (0.4-0.6), the defoamer is 902W, the leveling agent is BYK333 and the substrate wetting agent is 4100.
10. A fluorinated silica/aqueous epoxy resin composite anticorrosive paint obtained by the method for producing a fluorinated silica/aqueous epoxy resin composite anticorrosive paint according to any one of claims 1 to 9.
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