CN110484042B - Self-repairing super-hydrophobic nano anticorrosive coating and preparation method thereof - Google Patents
Self-repairing super-hydrophobic nano anticorrosive coating and preparation method thereof Download PDFInfo
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- CN110484042B CN110484042B CN201910605079.3A CN201910605079A CN110484042B CN 110484042 B CN110484042 B CN 110484042B CN 201910605079 A CN201910605079 A CN 201910605079A CN 110484042 B CN110484042 B CN 110484042B
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- 238000000576 coating method Methods 0.000 title claims abstract description 74
- 239000011248 coating agent Substances 0.000 title claims abstract description 71
- 230000003075 superhydrophobic effect Effects 0.000 title claims abstract description 33
- 238000002360 preparation method Methods 0.000 title claims abstract description 23
- 239000003094 microcapsule Substances 0.000 claims abstract description 55
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims abstract description 31
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims abstract description 24
- 239000004925 Acrylic resin Substances 0.000 claims abstract description 23
- 229920000178 Acrylic resin Polymers 0.000 claims abstract description 23
- 238000005260 corrosion Methods 0.000 claims abstract description 20
- 239000003054 catalyst Substances 0.000 claims abstract description 16
- 230000007797 corrosion Effects 0.000 claims abstract description 15
- 239000000203 mixture Substances 0.000 claims abstract description 13
- 230000002209 hydrophobic effect Effects 0.000 claims abstract description 12
- 229910052697 platinum Inorganic materials 0.000 claims abstract description 12
- 239000003112 inhibitor Substances 0.000 claims abstract description 11
- 239000002775 capsule Substances 0.000 claims abstract description 9
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 claims abstract description 8
- 238000002156 mixing Methods 0.000 claims abstract description 6
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims description 23
- 238000003756 stirring Methods 0.000 claims description 22
- 239000000243 solution Substances 0.000 claims description 20
- 229920001807 Urea-formaldehyde Polymers 0.000 claims description 12
- ODGAOXROABLFNM-UHFFFAOYSA-N polynoxylin Chemical compound O=C.NC(N)=O ODGAOXROABLFNM-UHFFFAOYSA-N 0.000 claims description 12
- 229910052681 coesite Inorganic materials 0.000 claims description 9
- 238000001816 cooling Methods 0.000 claims description 9
- 229910052906 cristobalite Inorganic materials 0.000 claims description 9
- 239000000839 emulsion Substances 0.000 claims description 9
- 239000000377 silicon dioxide Substances 0.000 claims description 9
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 9
- 229910052682 stishovite Inorganic materials 0.000 claims description 9
- 229910052905 tridymite Inorganic materials 0.000 claims description 9
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 8
- 239000004202 carbamide Substances 0.000 claims description 8
- 239000011259 mixed solution Substances 0.000 claims description 8
- 239000012964 benzotriazole Substances 0.000 claims description 6
- 230000001804 emulsifying effect Effects 0.000 claims description 6
- 238000005406 washing Methods 0.000 claims description 6
- 238000006243 chemical reaction Methods 0.000 claims description 5
- 238000001035 drying Methods 0.000 claims description 5
- 238000001914 filtration Methods 0.000 claims description 5
- 239000008098 formaldehyde solution Substances 0.000 claims description 5
- 239000003973 paint Substances 0.000 claims description 5
- 238000010790 dilution Methods 0.000 claims description 4
- 239000012895 dilution Substances 0.000 claims description 4
- 229920002396 Polyurea Polymers 0.000 claims description 3
- 239000004094 surface-active agent Substances 0.000 claims description 3
- 125000003354 benzotriazolyl group Chemical group N1N=NC2=C1C=CC=C2* 0.000 claims description 2
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 claims description 2
- 229920002545 silicone oil Polymers 0.000 claims description 2
- 238000009210 therapy by ultrasound Methods 0.000 claims description 2
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 claims 1
- 229910052731 fluorine Inorganic materials 0.000 claims 1
- 239000011737 fluorine Substances 0.000 claims 1
- 239000010703 silicon Substances 0.000 claims 1
- 239000011159 matrix material Substances 0.000 abstract description 13
- 238000000034 method Methods 0.000 abstract description 12
- 229920005989 resin Polymers 0.000 abstract description 12
- 239000011347 resin Substances 0.000 abstract description 12
- 230000000694 effects Effects 0.000 abstract description 11
- 230000008439 repair process Effects 0.000 abstract description 8
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 abstract description 7
- 239000008096 xylene Substances 0.000 abstract description 7
- 230000008569 process Effects 0.000 abstract description 6
- 239000006185 dispersion Substances 0.000 abstract description 2
- 238000011031 large-scale manufacturing process Methods 0.000 abstract description 2
- 229910004298 SiO 2 Inorganic materials 0.000 abstract 1
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 8
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 8
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 8
- 239000000178 monomer Substances 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- 239000003795 chemical substances by application Substances 0.000 description 7
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 230000009471 action Effects 0.000 description 6
- 238000010438 heat treatment Methods 0.000 description 6
- 238000007789 sealing Methods 0.000 description 6
- CIHOLLKRGTVIJN-UHFFFAOYSA-N tert‐butyl hydroperoxide Chemical compound CC(C)(C)OO CIHOLLKRGTVIJN-UHFFFAOYSA-N 0.000 description 6
- 238000004945 emulsification Methods 0.000 description 5
- 239000002245 particle Substances 0.000 description 5
- FGZFESWHQXSPJU-UHFFFAOYSA-N 2-methyl-2-(3,3,3-trifluoropropyl)-1,3,5,2,4,6-trioxatrisilinane Chemical compound FC(F)(F)CC[Si]1(C)O[SiH2]O[SiH2]O1 FGZFESWHQXSPJU-UHFFFAOYSA-N 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 4
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 4
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 description 4
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 4
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 description 4
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 4
- 238000009826 distribution Methods 0.000 description 4
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical group [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 description 4
- 239000003995 emulsifying agent Substances 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- FWDBOZPQNFPOLF-UHFFFAOYSA-N ethenyl(triethoxy)silane Chemical compound CCO[Si](OCC)(OCC)C=C FWDBOZPQNFPOLF-UHFFFAOYSA-N 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 4
- XWGJFPHUCFXLBL-UHFFFAOYSA-M rongalite Chemical compound [Na+].OCS([O-])=O XWGJFPHUCFXLBL-UHFFFAOYSA-M 0.000 description 4
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 description 4
- 239000000725 suspension Substances 0.000 description 4
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 239000012153 distilled water Substances 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 239000007764 o/w emulsion Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- 229910000831 Steel Inorganic materials 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- ZCDOYSPFYFSLEW-UHFFFAOYSA-N chromate(2-) Chemical compound [O-][Cr]([O-])(=O)=O ZCDOYSPFYFSLEW-UHFFFAOYSA-N 0.000 description 2
- 239000000306 component Substances 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000003595 mist Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
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- 239000002105 nanoparticle Substances 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 239000002861 polymer material Substances 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 239000011780 sodium chloride Substances 0.000 description 2
- LJRGBERXYNQPJI-UHFFFAOYSA-M sodium;3-nitrobenzenesulfonate Chemical compound [Na+].[O-][N+](=O)C1=CC=CC(S([O-])(=O)=O)=C1 LJRGBERXYNQPJI-UHFFFAOYSA-M 0.000 description 2
- 239000010959 steel Substances 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- 241000251730 Chondrichthyes Species 0.000 description 1
- 240000002853 Nelumbo nucifera Species 0.000 description 1
- 235000006508 Nelumbo nucifera Nutrition 0.000 description 1
- 235000006510 Nelumbo pentapetala Nutrition 0.000 description 1
- 239000011358 absorbing material Substances 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000000711 cancerogenic effect Effects 0.000 description 1
- 231100000315 carcinogenic Toxicity 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 239000008358 core component Substances 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
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- 238000002474 experimental method Methods 0.000 description 1
- ZHPNWZCWUUJAJC-UHFFFAOYSA-N fluorosilicon Chemical compound [Si]F ZHPNWZCWUUJAJC-UHFFFAOYSA-N 0.000 description 1
- 238000001453 impedance spectrum Methods 0.000 description 1
- 238000005272 metallurgy Methods 0.000 description 1
- 235000001968 nicotinic acid Nutrition 0.000 description 1
- 238000002161 passivation Methods 0.000 description 1
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- 238000006116 polymerization reaction Methods 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
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- 239000002893 slag Substances 0.000 description 1
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- 230000003068 static effect Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 238000001132 ultrasonic dispersion Methods 0.000 description 1
- 238000002604 ultrasonography Methods 0.000 description 1
Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J13/00—Colloid chemistry, e.g. the production of colloidal materials or their solutions, not otherwise provided for; Making microcapsules or microballoons
- B01J13/02—Making microcapsules or microballoons
-
- 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
- C09D143/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing boron, silicon, phosphorus, selenium, tellurium, or a metal; Coating compositions based on derivatives of such polymers
- C09D143/04—Homopolymers or copolymers of monomers containing silicon
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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
- 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
- C09D7/40—Additives
- C09D7/60—Additives non-macromolecular
- C09D7/61—Additives non-macromolecular inorganic
-
- 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
- C09D7/65—Additives macromolecular
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Inorganic Chemistry (AREA)
- Dispersion Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Paints Or Removers (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
本发明公开了一种自修复超疏水纳米防腐涂料及其制备方法，首先制备了一种微胶囊，然后将该微胶囊与有机氟硅改性丙烯酸树脂、疏水型纳米SiO2、二甲苯和铂基催化剂混匀后制备得到一种自修复超疏水纳米防腐涂料。本发明以甲基硅油和缓蚀剂的混合物为囊芯，不仅实现了缓蚀剂在基体树脂中的均匀分散，而且实现了涂层表面的自修复，可以有效避免服役和运输过程中的损失；本发明所述工艺简单，节能环保，适合大规模生产，将本发明的自修复超疏水纳米防腐涂料制成涂层后，涂层力学性能佳，防腐效果好，涂层的阻抗修复效率可达98％，断裂韧性修复效率可达99％。The invention discloses a self-healing super-hydrophobic nano anti-corrosion coating and a preparation method thereof. First, a microcapsule is prepared, and then the microcapsule is mixed with organofluorosilicon modified acrylic resin, hydrophobic nano-SiO 2 , xylene and platinum A self-healing superhydrophobic nano anti-corrosion coating is prepared after mixing the base catalyst. The invention uses the mixture of methyl silicone oil and the corrosion inhibitor as the capsule core, which not only realizes the uniform dispersion of the corrosion inhibitor in the matrix resin, but also realizes the self-repair of the coating surface, which can effectively avoid the loss during service and transportation; The process of the invention is simple, energy-saving and environmentally friendly, and is suitable for large-scale production. After the self-healing super-hydrophobic nano anti-corrosion coating of the invention is made into a coating, the coating has good mechanical properties, good anti-corrosion effect, and the impedance repairing efficiency of the coating can reach 98%, and the fracture toughness repair efficiency can reach 99%.
Description
Technical Field
The invention belongs to the technical field of anticorrosive coatings. In particular to a self-repairing super-hydrophobic nano anticorrosive coating and a preparation method thereof.
Background
The metal corrosion is one of the biggest challenges facing industries such as steel, metallurgy, construction, transportation and the like, and according to statistics, the direct economic loss caused by the corrosion of all countries in the world accounts for about 2% -4% of the total value of national production. There is also data indicating that for every second hand revolution of the watch, 1 ton of steel is corroded to slag in the world. Chromate has been conventionally used as a passivation layer for metal surface protection, but is clearly banned due to its extreme toxicity and carcinogenic characteristics, and thus the development of an environmentally friendly chromate-free coating protection technology is urgently needed.
With the development of technology, corrosion resistant coatings are considered to be the most effective means of replacing chromates. At present, the market scale of anticorrosive paint in China is second, and is second to architectural paint, and the annual demand speed is increased by more than 20%. However, during the service and transportation process, the coating is inevitably damaged by various external conditions, so that the phenomena of breakage and cracking are generated. Without timely and effective repair, these defects can significantly reduce the protective effect of the coating on the metal substrate and the adhesion of the coating. At present, the damaged coating is mainly repaired or replaced manually, and the process is complicated and the manufacturing cost is high.
In recent years, by using intelligent materials, the coating has the capability of self-repairing damage, and becomes a research hotspot in the field of corrosion protection at home and abroad, and has great application value. The self-repairing anticorrosive coating can automatically recover or recover the original anticorrosive function under certain conditions after being damaged by external force or environment. The microcapsule filled self-repairing coating is a common self-repairing coating at present, a repairing agent is encapsulated in microcapsules, the microcapsules and a catalyst capable of polymerizing the repairing agent are compounded in a polymer material, when a polymer generates cracks in the polymer material under the action of the outside, the microcapsules are broken under the action of the cracks, the repairing agent is released under the action of siphonage and fills the cracks, and then the repairing agent reacts with the catalyst in a base material to initiate polymerization, so that the cracks are repaired, and the performance of the coating is recovered. However, the microcapsule core has single component and is mostly single resin, the self-repairing effect is not ideal, the mechanical property is not good, and the bonding force with the matrix resin is poor. And the emulsion is difficult to stabilize in the traditional microcapsule preparation method, so that the coating efficiency is not high.
The super-hydrophobic technology belongs to the field of nanotechnology and bionics. Theoretically, superhydrophobic refers to a state where a static contact angle is 150 ° or more and a rolling angle is less than 10 °, and typical examples thereof include a lotus leaf surface, shark skin, and the like. After the super-hydrophobic coating is coated on the surface of an object, the anti-corrosion and self-cleaning functions are achieved. Therefore, the development of the anticorrosive coating with the double effects of super hydrophobicity and self-repair can ensure the long-acting anticorrosive effect of the coating, and the anticorrosive coating has no loss in the service and transportation processes and has wide application prospect.
Disclosure of Invention
The invention aims to overcome the defects and shortcomings of the prior art, provides a preparation method of microcapsules, aims to solve the problems of single capsule core component and poor mechanical property of the conventional microcapsules, and uses the microcapsules prepared by the method to prepare the self-repairing super-hydrophobic nano anticorrosive coating with good mechanical property.
The second purpose of the invention is to provide the microcapsule prepared by the method.
The third purpose of the invention is to provide a self-repairing super-hydrophobic nano anticorrosive coating.
The fourth purpose of the invention is to provide a preparation method of the self-repairing super-hydrophobic nano anticorrosive coating.
The above purpose of the invention is realized by the following technical scheme:
a microcapsule, wherein the capsule core of the microcapsule is a mixture of dimethyl silicone oil and a corrosion inhibitor, and the capsule wall is polyurea formaldehyde.
The microcapsule disclosed by the invention has good binding property with matrix resin, the binding force reaches 6-7 MPa, and the microcapsule has high sealing property.
The microcapsule prepared by using the polyurea formaldehyde as the capsule wall and the mixture of the methyl silicone oil and the corrosion inhibitor benzotriazole as the capsule core has the advantages of concentrated and controllable particle size distribution, stable thickness and regular shape.
Preferably, the corrosion inhibitor is benzotriazole.
The preparation method of the microcapsule comprises the following steps:
s1, preparing a urea-formaldehyde prepolymer solution from urea and formaldehyde;
s2, mixing the urea-formaldehyde prepolymer, the methyl silicone oil and the corrosion inhibitor according to the mass ratio of (80-100): (8-10): (4-5) uniformly mixing, emulsifying, polycondensing, washing, filtering and drying to obtain the catalyst.
Preferably, in the step S1, the urea and the formaldehyde solution are mixed according to the mass ratio (0.5-1.5): (1.5-2.5), adjusting the pH value of the mixed solution to 8.0-9.0, placing the mixed solution at the temperature of 60-80 ℃ for reaction for 0.5-1.5 h, cooling, and adding a surfactant with the mass fraction of 0.6-1.3% for dilution to obtain the urea-formaldehyde prepolymer solution.
Preferably, the urea and formaldehyde solutions are mixed in a mass ratio of 1: 2.
Preferably, in step S1, the pH-adjusted solution is triethanolamine.
Preferably, in step S1, the surfactant is sodium dodecylbenzenesulfonate.
Preferably, the emulsification in the step S2 is carried out for 40-50 min at 30-40 ℃.
Preferably, the pH of the emulsion is adjusted to 2.0-2.5 in the step S2, and the emulsion is reacted for 3-4 h at 70-75 ℃.
Preferably, in step S2, the pH adjusting solution is sulfuric acid.
Preferably, the washing solution is xylene, absolute ethanol and water, so that the suspension is washed clean to obtain pure microcapsules.
The microcapsule prepared by the invention has good wrapping property, good binding property with matrix resin and higher sealing property, and can effectively improve the self-repairing effect of the self-repairing coating after being added into the coating. Therefore, the invention requests to protect the application of the microcapsule in the preparation of the self-repairing super-hydrophobic nano anticorrosive coating.
A self-repairing super-hydrophobic nano anticorrosive paint is prepared from organic fluorosilicone modified acrylic resin and hydrophobic nano SiO2The microcapsule, the dimethylbenzene and the platinum-based catalyst are mixed uniformly.
Preferably, the organic fluorine-silicon modified acrylic resin, xylene and hydrophobic nano SiO2The mass ratio of the microcapsule to the platinum-based catalyst is (80-100): (20-30): (0.8-2): (8-20): (1-5).
In the anticorrosive paint, organic fluorine-silicon modified acrylic resin is used as a matrix and a film forming substance, xylene is used as a solvent, microcapsules are used as a self-repairing component, and hydrophobic nano SiO is used2The platinum-based catalyst is used for being compounded with matrix resin, further enhancing the hydrophobicity of the surface of the coating, endowing the coated surface with better wear resistance and weather resistance, and carrying out crosslinking curing reaction with a repairing agent to repairThe crack surface realizes the self-repair of the damaged part.
The self-repairing function of the coating is realized by the following steps: when the coating cracks, the microcapsules can crack along with the cracks and release the repairing agent, and the repairing agent is combined with the platinum-based catalyst; the microcapsule disclosed by the invention has good compatibility with the organic fluorine-silicon modified acrylic resin, and can efficiently seal cracks, so that a self-repairing function is realized.
In addition, the preparation method of the self-repairing super-hydrophobic nano anticorrosive coating is also within the protection scope of the invention, and the preparation method comprises the following steps: organic fluorine-silicon modified acrylic resin, dimethylbenzene and hydrophobic nano SiO2The microcapsule and the platinum-based catalyst are mixed according to the mass ratio (80-100): (20-30): (0.8-2): (8-20): (1-5), stirring at 1000-1500 rpm for 1-2 h, and then carrying out ultrasonic treatment for 30-40 min under the condition of 300-500W to obtain the ultrasonic wave-absorbing material.
More preferably, the organic fluorine-silicon modified acrylic resin, xylene and hydrophobic nano SiO2The mass ratio of the microcapsule to the platinum-based catalyst is (80-100): (20-30): (1-2): (8-10): (2-4).
Preferably, the hydrophobic nano SiO2The particle size of (A) is 20 to 50 nm.
According to the invention, the organic fluorine-silicon modified acrylic resin is used as a matrix, the microcapsule and the nano particles are added to form the super-hydrophobic coating, the microcapsule has good compatibility with the matrix resin and higher sealing performance, and the self-repairing effect of the self-repairing coating can be effectively improved after the microcapsule is added to the coating; the flexibility, hardness and water resistance of the acrylic resin modified by the fluorine silicon become better, the fluorinated modified acrylic resin has a super-hydrophobic effect, the matrix resin is compounded with the nano particles, the hydrophobicity of the surface of the coating is further enhanced, and the coated surface is endowed with better wear resistance and weather resistance.
Preferably, the preparation method of the organic fluorine-silicon modified acrylic resin comprises the steps of firstly adding 200-250 g of dimethylbenzene and 6-10 g of emulsifier sodium dodecyl sulfate into a reactor, heating to 70 ℃, and fully stirring for dissolving; premixing 200g of methyl methacrylate, 100-150 g of butyl acrylate and 70-80 g of alpha-methacrylic acid in another flask, taking out 1/10 of an acrylate monomer mixture, adding the mixture into a reactor for pre-emulsification for 0.5-2 h, adding 3-5 g of potassium persulfate, stirring for 5-10 min, after seed emulsion is formed, beginning to dropwise add the rest of the acrylate monomer mixed solution, 30-50 g of vinyltriethoxysilane and 25-50 g of trifluoropropylmethyl cyclotrisiloxane, adding 1-2 g of tert-butyl hydroperoxide and 1-2 g of rongalite, keeping the temperature, continuing to react for 1h, and cooling to obtain the organofluorosilicone modified acrylic resin.
The inventor prepares a self-repairing super-hydrophobic nano anticorrosive coating through creative labor, the coating has double effects of super-hydrophobicity and self-repairing, the contact angle of the coating surface is larger than 150 degrees and greatly exceeds that of a common coating, the super-hydrophobic property of the coating surface enables water molecules to be difficult to enter the coating, and the anticorrosive property of the coating is further improved.
Compared with the prior art, the invention has the following beneficial effects:
the microcapsule takes the mixture of methyl silicone oil and the corrosion inhibitor as the capsule core, not only realizes the uniform dispersion of the corrosion inhibitor in matrix resin, but also realizes the self-repairing of the coating surface, and can effectively avoid the loss in service and transportation processes; the method has the advantages of simple process, energy conservation, environmental protection and suitability for large-scale production; after the self-repairing super-hydrophobic nano anticorrosive coating is prepared into a coating, the mechanical property of the coating is good, the adhesive force can reach 8Mpa, the impact resistance is 100cm, and the flexibility is 1 mm; the coating has good anticorrosion effect, can resist salt mist for 3000H, moisture and heat for 2000H and 10% H2SO4960h, 960h for 10 percent NaOH, 720h for 3 percent NaCl and 600h for 93# gasoline, and the obtained coating has the impedance repair efficiency of 98 percent and the fracture toughness repair efficiency of 99 percent.
Detailed Description
The present invention is further illustrated by the following specific examples, which are not intended to limit the invention in any way. Reagents, methods and apparatus used in the present invention are conventional in the art unless otherwise indicated.
Unless otherwise indicated, reagents and materials used in the following examples are commercially available.
Example 1
(1) Preparation of organic fluorine-silicon modified acrylic resin
200g of xylene and 8g of emulsifier sodium dodecyl sulfate are added into a reactor, heated to 70 ℃, and fully stirred to be dissolved. Premixing 200g of methyl methacrylate, 150g of butyl acrylate and 70g of alpha-methacrylic acid in another flask, taking out 1/10 of acrylate monomer mixture, adding the mixture into a reactor for pre-emulsification for 0.5h, adding 3g of potassium persulfate, stirring for 5min, after seed emulsion is formed, beginning to dropwise add the remaining acrylate monomer mixed solution, 50g of vinyl triethoxysilane and 25g of trifluoropropyl methyl cyclotrisiloxane, then adding 1g of tert-butyl hydroperoxide and 1g of rongalite, keeping the temperature, continuing to react for 1h, and cooling to obtain the organic fluorosilicone modified acrylic resin.
(2) Preparation of microcapsules
Adding 50g of urea and 100g of formaldehyde solution into a four-neck flask at room temperature, stirring and dissolving, then adjusting the pH value of the solution to 8.0 by using triethanolamine, reacting at 70 ℃ for 1h to obtain a viscous and transparent urea-formaldehyde prepolymer, quickly cooling, and adding 100g of aqueous solution containing 1g of sodium dodecyl benzene sulfonate under the stirring action for dilution to obtain a urea-formaldehyde prepolymer solution; adding 80g of prepolymer solution into a four-neck flask, adding 8g of methyl silicone oil and 4g of benzotriazole while stirring, stirring and emulsifying at 35 ℃ for 40min to obtain an oil-in-water (O/W) emulsion, slowly adjusting the pH value to 2.0 by using a sulfuric acid solution, slowly heating to 70 ℃ for reaction for 3h, washing the obtained suspension by using dimethylbenzene, absolute ethyl alcohol and distilled water, filtering and drying to obtain a microcapsule; the prepared microcapsule has centralized and controllable particle size distribution, stable thickness and regular shape; the microcapsule has strong bonding property with matrix resin, the bonding force reaches 7MPa, and the microcapsule has higher sealing property,
(3) preparation of self-repairing super-hydrophobic coating
100g of organic fluorine-silicon modified acrylic resin, 20g of dimethylbenzene and 1g of hydrophobic nano SiO210g of microcapsule and 4g of platinum-based catalyst, stirring for 1h at 1000rpm, and then performing ultrasonic dispersion for 30min at 500w to obtain the catalystThe super-hydrophobic coating has a self-repairing effect.
Example 2
(1) Preparation of organic fluorine-silicon modified acrylic resin
Adding 250g of dimethylbenzene and 10g of emulsifier sodium dodecyl sulfate into a reactor, heating to 70 ℃, and fully stirring for dissolving; premixing 200g of methyl methacrylate, 150g of butyl acrylate and 70g of alpha-methacrylic acid in another flask, taking out 1/10 of acrylate monomer mixture, adding the mixture into a reactor for pre-emulsification for 1 hour, adding 5g of potassium persulfate, stirring for 10min, after seed emulsion is formed, dropwise adding the rest of acrylate monomer mixed solution, 50g of vinyltriethoxysilane and 50g of trifluoropropylmethyl cyclotrisiloxane, adding 2g of tert-butyl hydroperoxide and 2g of rongalite, keeping the temperature, continuing to react for 1 hour, and cooling to obtain the organofluorosilicone modified acrylic resin.
(2) Preparation of microcapsules
Adding 70g of urea and 140g of formaldehyde solution into a four-neck flask at room temperature, stirring and dissolving, then adjusting the pH value of the solution to 9.0 by using triethanolamine, reacting at 70 ℃ for 1h to obtain a viscous and transparent urea-formaldehyde prepolymer, quickly cooling, and adding 150g of aqueous solution containing 2g of sodium dodecyl benzene sulfonate under the stirring action for dilution to obtain a urea-formaldehyde prepolymer solution; adding 100g of prepolymer solution into a four-neck flask, adding 10g of methyl silicone oil and 5g of benzotriazole while stirring, stirring and emulsifying at 35 ℃ for 50min to obtain an oil-in-water (O/W) emulsion, slowly adjusting the pH to 2.5 with a sulfuric acid solution, slowly heating to 75 ℃ to react for 4h, washing the obtained suspension with xylene, absolute ethyl alcohol and distilled water, filtering and drying to obtain a microcapsule; the prepared microcapsule has centralized and controllable particle size distribution, stable thickness and regular shape; the microcapsule has strong bonding property with matrix resin, the bonding force reaches 6MPa, and the microcapsule has higher sealing property.
(3) Preparation of self-repairing super-hydrophobic coating
80g of organic fluorine-silicon modified acrylic resin, 20g of dimethylbenzene and 2g of hydrophobic nano SiO28g of microcapsule and 3g of platinum-based catalyst are mixed, stirred for 1h at 1500rpm and then ultrasonically dispersed for 40min at 300w to obtain the super-hydrophobic material with self-repairing effectAnd (5) water coating.
Example 3
(1) Preparation of organic fluorine-silicon modified acrylic resin
Adding 200g of dimethylbenzene and 6g of emulsifier sodium dodecyl sulfate into a reactor, heating to 70 ℃, and fully stirring for dissolving; premixing 200g of methyl methacrylate, 100g of butyl acrylate and 80g of alpha-methacrylic acid in another flask, taking out 1/10 of acrylate monomer mixture, adding the mixture into a reactor for pre-emulsification for 2 hours, adding 4g of potassium persulfate, stirring for 10 minutes, after seed emulsion is formed, dropwise adding the rest of acrylate monomer mixed solution, 30g of vinyltriethoxysilane and 30g of trifluoropropylmethyl cyclotrisiloxane, adding 1g of hydrogen peroxide tert-butyl alcohol and 2g of rongalite, keeping the temperature, continuing to react for 1 hour, and cooling to obtain the organofluorosilicone modified acrylic resin.
(2) Preparation of microcapsules
Adding 50g of urea and 100g of formaldehyde solution into a four-neck flask at room temperature, stirring for dissolving, then adjusting the pH value of the solution to 8.5 by using triethanolamine, reacting at 70 ℃ for 1h to obtain a viscous and transparent urea-formaldehyde prepolymer, quickly cooling, and adding 80g of aqueous solution containing 0.5g of sodium dodecyl benzene sulfonate under the stirring action for diluting to obtain a urea-formaldehyde prepolymer solution; adding 80g of prepolymer solution into a four-neck flask, adding 10g of methyl silicone oil and 4g of benzotriazole while stirring, stirring and emulsifying at 35 ℃ for 40min to obtain an oil-in-water (O/W) emulsion, slowly adjusting the pH value to 2.5 by using a sulfuric acid solution, slowly heating to 73 ℃ for reaction for 4h, washing the obtained suspension by using dimethylbenzene, absolute ethyl alcohol and distilled water, filtering and drying to obtain a microcapsule; the prepared microcapsule has centralized and controllable particle size distribution, stable thickness and regular shape; the microcapsule has strong bonding property with matrix resin, the bonding force reaches 6MPa, and the microcapsule has higher sealing property.
(3) Preparation of self-repairing super-hydrophobic coating
100g of organic fluorine-silicon modified acrylic resin, 30g of dimethylbenzene and 1.5g of hydrophobic nano SiO210g of microcapsule and 2g of platinum-based catalyst are mixed, stirred for 2 hours at 1500rpm, and then dispersed for 30 minutes by 400w of ultrasound to obtain the super-hydrophobic coating with the self-repairing effect.
Performance testing
Method and device
The self-repairing super-hydrophobic nano anticorrosive coating obtained in the embodiment 1-3 is subjected to performance test according to the following methods:
the adhesion force is tested according to the GB/T1720-;
impact resistance as per GB/T1732-1993;
flexibility is tested according to GB/T1720-79 standard;
the salt water resistance is tested according to the GB/T1763-89 standard;
gasoline resistance was tested according to GB/T1734 + 1993 standard;
the salt spray resistance is tested according to the GB/T1771-91 standard;
the acid and alkali resistance is tested according to the GB/T1763 standard;
the humidity and heat resistance is tested according to the GB/T1740 standard;
contact angle test: measuring with a contact angle measuring instrument;
testing the impedance repairing efficiency before and after the coating is repaired by utilizing an electrochemical alternating current impedance spectrum technology;
and measuring the fracture toughness repairing efficiency before and after the coating is repaired by utilizing an impact pendulum bob experiment machine.
Second, result in
Relevant performance indexes of the self-repairing super-hydrophobic nano anticorrosive coating prepared into the coating are respectively shown in the following tables 1, 2 and 3.
TABLE 1 determination results of relevant indexes of self-repairing super-hydrophobic nano anticorrosive coating
TABLE 2 determination results of relevant indexes of self-repairing super-hydrophobic nano anticorrosive coating
TABLE 3 self-repair Performance test results for self-repair coatings
| Efficiency of impedance repair (%) | Fracture toughness repair efficiency (%) | |
| Example 1 | 98 | 99 |
| Example 2 | 95 | 97 |
| Example 3 | 94 | 95 |
As can be seen from the above tables 1-3, after the self-repairing super-hydrophobic nano anticorrosive coating is prepared into a coating, the coating has good mechanical property, the adhesive force can reach 8Mpa, the impact resistance is 100cm, and the flexibility is 1 mm; the coating has good anticorrosion effect, can resist salt mist for 3000H, moisture and heat for 2000H and 10% H2SO4960h, 960h for resisting 10% NaOH, 720h for resisting 3% NaCl and 600h for resisting 93# gasoline; in addition, the impedance repair efficiency of the obtained coating can reach 98%, and the fracture toughness repair efficiency can reach 99%.
The above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents thereof, and all such changes, modifications, substitutions, combinations, and simplifications are intended to be included in the scope of the present invention.
Claims (1)
1. The self-repairing super-hydrophobic nano anticorrosive paint is characterized by comprising organic fluorine-silicon modified acrylic resin and hydrophobic nano SiO2The microcapsule, the dimethylbenzene and the platinum-based catalyst are mixed evenly; the preparation method of the self-repairing super-hydrophobic nano anticorrosive coating comprises the steps of modifying acrylic resin, dimethylbenzene and hydrophobic nano SiO with organic fluorine and silicon2The microcapsule and the platinum-based catalyst are mixed according to the mass ratio (80-100): (20-30): (1-2): (8-10): (2-4) stirring at 1000-1500 rpm for 1-2 h after mixing, and then carrying out ultrasonic treatment for 30-40 min under the condition of 300-500W to obtain the product;
the capsule core of the microcapsule is a mixture of dimethyl silicone oil and a corrosion inhibitor, and the capsule wall of the microcapsule is polyurea formaldehyde; the corrosion inhibitor is benzotriazole;
the preparation method of the microcapsule comprises the following steps:
s1, preparing a urea-formaldehyde prepolymer solution from urea and formaldehyde;
s2, mixing the urea-formaldehyde prepolymer, the methyl silicone oil and the corrosion inhibitor according to the mass ratio of (80-100): (8-10): (4-5) uniformly mixing, emulsifying, polycondensing, washing, filtering and drying to obtain the catalyst;
step S1, urea and formaldehyde solution are mixed according to the mass ratio (0.5-1.5): (1.5-2.5), adjusting the pH value of the mixed solution to 8.0-9.0, placing the mixed solution at the temperature of 60-80 ℃ for reaction for 0.5-1.5 h, cooling, and adding a surfactant with the mass fraction of 0.6-1.3% for dilution to obtain a urea-formaldehyde prepolymer solution;
emulsifying in the step S2 to emulsify for 40-50 min at 30-40 ℃;
in the step S2, the pH of the emulsion is adjusted to 2.0-2.5, and the emulsion is reacted for 3-4 hours at 70-75 ℃.
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