CN116606581B - Lightweight high-solid epoxy heavy-duty anticorrosive paint and preparation method thereof - Google Patents
Lightweight high-solid epoxy heavy-duty anticorrosive paint and preparation method thereof Download PDFInfo
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- 239000004593 Epoxy Substances 0.000 title claims abstract description 36
- 239000007787 solid Substances 0.000 title claims abstract description 26
- 239000003973 paint Substances 0.000 title claims abstract description 23
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 33
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 31
- 239000002002 slurry Substances 0.000 claims abstract description 26
- 239000002131 composite material Substances 0.000 claims abstract description 18
- 239000000945 filler Substances 0.000 claims abstract description 17
- 239000003822 epoxy resin Substances 0.000 claims abstract description 16
- 229920000647 polyepoxide Polymers 0.000 claims abstract description 16
- 239000002904 solvent Substances 0.000 claims abstract description 12
- 239000000539 dimer Substances 0.000 claims abstract description 11
- 239000000843 powder Substances 0.000 claims abstract description 11
- 239000002253 acid Substances 0.000 claims abstract description 10
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 9
- -1 aminosilane modified 1, 6-hexanediol diglycidyl ether Chemical class 0.000 claims abstract description 9
- 239000004841 bisphenol A epoxy resin Substances 0.000 claims abstract description 9
- 239000002270 dispersing agent Substances 0.000 claims abstract description 9
- FZHAPNGMFPVSLP-UHFFFAOYSA-N silanamine Chemical compound [SiH3]N FZHAPNGMFPVSLP-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000002518 antifoaming agent Substances 0.000 claims abstract description 7
- 239000013008 thixotropic agent Substances 0.000 claims abstract description 5
- 235000019832 sodium triphosphate Nutrition 0.000 claims abstract description 4
- UNXRWKVEANCORM-UHFFFAOYSA-I triphosphate(5-) Chemical compound [O-]P([O-])(=O)OP([O-])(=O)OP([O-])([O-])=O UNXRWKVEANCORM-UHFFFAOYSA-I 0.000 claims abstract description 4
- 238000006243 chemical reaction Methods 0.000 claims description 18
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 11
- SJECZPVISLOESU-UHFFFAOYSA-N 3-trimethoxysilylpropan-1-amine Chemical compound CO[Si](OC)(OC)CCCN SJECZPVISLOESU-UHFFFAOYSA-N 0.000 claims description 10
- 150000001412 amines Chemical class 0.000 claims description 10
- 238000003756 stirring Methods 0.000 claims description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 9
- FPAFDBFIGPHWGO-UHFFFAOYSA-N dioxosilane;oxomagnesium;hydrate Chemical compound O.[Mg]=O.[Mg]=O.[Mg]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O FPAFDBFIGPHWGO-UHFFFAOYSA-N 0.000 claims description 8
- 238000000034 method Methods 0.000 claims description 8
- 239000011324 bead Substances 0.000 claims description 7
- 239000010456 wollastonite Substances 0.000 claims description 7
- 229910052882 wollastonite Inorganic materials 0.000 claims description 7
- 239000004952 Polyamide Substances 0.000 claims description 6
- 238000001914 filtration Methods 0.000 claims description 6
- 229910052757 nitrogen Inorganic materials 0.000 claims description 6
- 229920002647 polyamide Polymers 0.000 claims description 6
- 239000008367 deionised water Substances 0.000 claims description 5
- 229910021641 deionized water Inorganic materials 0.000 claims description 5
- 239000011521 glass Substances 0.000 claims description 5
- 230000004048 modification Effects 0.000 claims description 5
- 238000012986 modification Methods 0.000 claims description 5
- WTYYGFLRBWMFRY-UHFFFAOYSA-N 2-[6-(oxiran-2-ylmethoxy)hexoxymethyl]oxirane Chemical compound C1OC1COCCCCCCOCC1CO1 WTYYGFLRBWMFRY-UHFFFAOYSA-N 0.000 claims description 4
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 4
- 238000007667 floating Methods 0.000 claims description 4
- 238000004806 packaging method and process Methods 0.000 claims description 4
- 229920000570 polyether Polymers 0.000 claims description 4
- 230000008569 process Effects 0.000 claims description 4
- 244000226021 Anacardium occidentale Species 0.000 claims description 3
- 235000020226 cashew nut Nutrition 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 claims description 3
- 239000003921 oil Substances 0.000 claims description 3
- 238000005406 washing Methods 0.000 claims description 3
- 239000013530 defoamer Substances 0.000 claims description 2
- 238000004321 preservation Methods 0.000 claims description 2
- 239000002994 raw material Substances 0.000 claims description 2
- 239000011248 coating agent Substances 0.000 abstract description 81
- 238000000576 coating method Methods 0.000 abstract description 81
- 239000004005 microsphere Substances 0.000 abstract description 11
- 230000002195 synergetic effect Effects 0.000 abstract description 4
- 230000005764 inhibitory process Effects 0.000 abstract description 2
- 238000005260 corrosion Methods 0.000 description 21
- 230000007797 corrosion Effects 0.000 description 17
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 14
- 230000000052 comparative effect Effects 0.000 description 10
- 230000000694 effects Effects 0.000 description 10
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 9
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 9
- 238000005516 engineering process Methods 0.000 description 8
- 239000012046 mixed solvent Substances 0.000 description 8
- 239000000126 substance Substances 0.000 description 8
- 238000013461 design Methods 0.000 description 6
- 238000010907 mechanical stirring Methods 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- 239000000758 substrate Substances 0.000 description 6
- 229920005989 resin Polymers 0.000 description 5
- 239000011347 resin Substances 0.000 description 5
- 239000000463 material Substances 0.000 description 4
- 230000009467 reduction Effects 0.000 description 4
- 238000011160 research Methods 0.000 description 4
- 239000006087 Silane Coupling Agent Substances 0.000 description 3
- 238000004132 cross linking Methods 0.000 description 3
- 229910052710 silicon Inorganic materials 0.000 description 3
- 239000010703 silicon Substances 0.000 description 3
- 238000001179 sorption measurement Methods 0.000 description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000002860 competitive effect Effects 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 125000003700 epoxy group Chemical group 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000004814 polyurethane Substances 0.000 description 2
- 229920002635 polyurethane Polymers 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 239000013585 weight reducing agent Substances 0.000 description 2
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
- 238000005411 Van der Waals force Methods 0.000 description 1
- 241000276425 Xiphophorus maculatus Species 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 239000000440 bentonite Substances 0.000 description 1
- 229910000278 bentonite Inorganic materials 0.000 description 1
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical group O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 125000003636 chemical group Chemical group 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000011247 coating layer Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 238000005536 corrosion prevention Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 229920006334 epoxy coating Polymers 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 239000003562 lightweight material Substances 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
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- 230000036961 partial effect Effects 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000000967 suction filtration Methods 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Classifications
-
- 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
- C09D163/00—Coating compositions based on epoxy resins; Coating compositions based on derivatives of epoxy resins
- C09D163/10—Epoxy resins modified by unsaturated compounds
-
- 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
- C09D5/10—Anti-corrosive paints containing metal dust
- C09D5/103—Anti-corrosive paints containing metal dust containing Al
-
- 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
- C09D7/60—Additives non-macromolecular
- C09D7/61—Additives non-macromolecular inorganic
- C09D7/62—Additives non-macromolecular inorganic modified by treatment with other compounds
-
- 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
-
- 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
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/02—Elements
- C08K3/08—Metals
- C08K2003/0812—Aluminium
-
- 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
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
- C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
- Y02W30/50—Reuse, recycling or recovery technologies
- Y02W30/91—Use of waste materials as fillers for mortars or concrete
Landscapes
- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Paints Or Removers (AREA)
Abstract
The invention relates to the technical field of paint, in particular to a lightweight high-solid epoxy heavy-duty anticorrosive paint and a preparation method thereof. The light high-solid epoxy heavy-duty anticorrosive paint comprises a component A and a component B, wherein the component A comprises bisphenol A epoxy resin, aminosilane modified dimer acid modified epoxy resin, aminosilane modified 1, 6-hexanediol diglycidyl ether, a dispersing agent, a leveling agent, a defoaming agent, sericite powder, a filler, aluminum tripolyphosphate, a modified hollow microsphere-flaky aluminum powder slurry composite material, a solvent and a thixotropic agent; the component B comprises a curing agent; the mass ratio of the component A to the component B is 8-11:1. According to the lightweight high-solid epoxy heavy-duty anticorrosive coating provided by the invention, the coating thickness is reduced while the coating density is reduced through the synergistic effect of the lightweight hollow microspheres, the low-density filler and the cathode stripping inhibition filler aluminum powder slurry, so that the coating is lightweight, and the coating is ensured to have excellent cathode stripping resistance under the lightweight condition.
Description
Technical Field
The invention relates to the technical field of paint, in particular to a lightweight high-solid epoxy heavy-duty anticorrosive paint and a preparation method thereof.
Background
The strength of offshore military forces mainly depends on a high-precision positioning navigation system, a precise striking capability, a stealth technology, a rapid sailing speed and the like. The sailing speed is mainly limited by the weight of equipment besides the streamline design, the power design and the drag reduction technology of the equipment. Therefore, the weight reduction of the whole structure in the design of the military vessel is a key technology for manufacturing.
The existing coating used by military equipment is a traditional coating, the performances of corrosion resistance, environmental protection and the like of the coating are emphasized in the formula design of the coating, the lightweight design is not involved, the density of the whole coating system is large, the quality is large, and the navigational speed is greatly influenced. Therefore, the development of drag reduction, speed increase and weight reduction has become a mainstream trend.
The foreign company has developed partial lightweight coating mainly comprising polyurethane, epoxy acrylic polyurethane and epoxy modified acrylic, the research of epoxy lightweight coating is rarely reported in foreign countries, and the research of different types of lightweight coating is rarely performed at present in China, mainly because the epoxy coating is applied to the heavy corrosion prevention field, and the reduction of the coating density or the thickness of the coating reduces the weight of the coating and simultaneously the original corrosion resistance of the coating is difficult to ensure.
The main technical approaches of coating lightening are two, namely, lightening materials are adopted to replace traditional materials, so that the density of the coating is reduced; secondly, the coating thickness of the coating is reduced, and the coating quality per unit area is reduced. However, the light-weight materials are less in variety, the use amount is less, the light-weight is limited, the dispersibility is poor and the corrosion resistance is reduced due to the use amount more, and the coating thickness of the coating is reduced, so that the coating protection effect is inevitably reduced, and particularly the cathode stripping resistance of the coating is greatly influenced.
Therefore, how to prepare a lightweight coating layer excellent in cathodic disbonding resistance has become a hot spot of research.
Disclosure of Invention
In order to solve the defect that the coating in the prior art cannot meet the requirements of light weight and cathode stripping resistance simultaneously, the invention provides a light weight high-solid epoxy heavy anti-corrosion coating, which comprises the following raw materials in parts by mass
The component B comprises a curing agent;
the mass ratio of the component A to the component B is 8-11:1.
In some embodiments, the bisphenol A epoxy resin has an epoxy equivalent weight of 180-200g/eq.
In some embodiments, the solvent is a mixed solvent of xylene and n-butanol.
In some embodiments, the aminosilane-modified dimer acid-modified epoxy resin is specifically modified by:
adding 100 parts of dimer acid modified epoxy resin and 0.1 part of K54 into a reaction container in parts by weight, and stirring; then introducing nitrogen for 30min, heating to 50-60 ℃, dropwise adding 25.0 parts of gamma-aminopropyl trimethoxy silane solution for 1.0h, and then carrying out heat preservation reaction for 2.0h to obtain the aminosilane modified dimer acid modified epoxy resin. Specifically, the reaction vessel can be a 250m l four-neck flask with a mechanical stirring device and a condenser pipe, and condensed water is started while stirring, so that the reaction is controlled to be carried out normally.
Preferably, the dimer acid modified epoxy resin is a commercial EPD-171 difunctional epoxy resin, and the epoxy equivalent of the dimer acid modified epoxy resin is 400-500g/eq;
in some embodiments, the aminosilane-modified 1, 6-hexanediol diglycidyl ether is prepared by:
100 parts of 1, 6-hexanediol diglycidyl ether and 0.1 part of K54 are added into a reaction vessel in parts by mass, stirring is carried out, nitrogen is introduced for 30min, the temperature is raised to 50-60 ℃, 50.0 parts of gamma-aminopropyl trimethoxysilane solution is dropwise added for 1.0h, and then the reaction is carried out for 2.0h in a heat-preserving way, thus obtaining the aminosilane modified 1, 6-hexanediol diglycidyl ether. Specifically, the reaction vessel can be a 250m l four-neck flask with a mechanical stirring device and a condenser pipe, and condensed water is started while stirring, so that the reaction is controlled to be carried out normally.
Preferably, the mass concentration of the gamma-aminopropyl trimethoxy silane solution is 20%, and the solvent of the gamma-aminopropyl trimethoxy silane solution adopts a mixed solvent of absolute ethyl alcohol and water in a volume ratio of 10:1; after dissolving the gamma-aminopropyl trimethoxy silane solution in a solvent, regulating the PH to 4 by acetic acid, sealing and standing for 1h, and regulating the PH to 7 to obtain the gamma-aminopropyl trimethoxy silane solution.
In some embodiments, the dispersant includes any of BYK-110, UKa 710S.
In some embodiments, the leveling agent includes any one of BYK-354, ucat 384S.
In some embodiments, the defoamer includes any of BYK-A530, UKa 272S.
In some embodiments, the modified hollow microsphere-sheet aluminum slip composite modification process is:
100 parts of aluminum powder slurry is placed in a reaction container, 80 parts of KH560 solution with the mass fraction of 10% is added, the temperature is controlled to be 40-45 ℃, and 2500r/min is dispersed for 40min at a high speed; adding 500 parts of absolute ethyl alcohol and 100 parts of 500-mesh hollow glass beads or floating beads, and continuing to keep the temperature and disperse at a high speed for 40min;
and filtering to remove absolute ethyl alcohol in the product, washing with deionized water, and drying to obtain the modified hollow microsphere-flaky aluminum powder slurry composite material. In particular, the method comprises the steps of,
preferably, the solvent of KH560 solution with mass fraction of 10% adopts mixed solvent of absolute ethanol and deionized water with volume ratio of 10:1, and after the preparation is completed, PH of KH560 solution is adjusted to 4 by acetic acid.
In some embodiments, the filler is one or any of talc powder and wollastonite powder.
Preferably, the filler is a combination of talcum powder and wollastonite powder, and the mass ratio of talcum powder to wollastonite powder is 3-2:1.
In some embodiments, the thixotropic agent is a polyamide wax.
In some embodiments, the curing agent is any one or a combination of a polyether amine curing agent, a cashew nut shell oil modified amine curing agent, an alicyclic amine curing agent
Preferably, the alicyclic amine curing agent has an amine value of 200-250 mgKOH/g, the polyether amine curing agent has an amine value of 342-370 mgKOH/g, and the cashew shell oil modified amine curing agent has an amine value of 385-420 mgKOH/g.
The invention also provides a method for preparing the lightweight high-solid epoxy heavy-duty anticorrosive paint, which comprises the following steps:
the preparation method of the component A comprises the following steps:
adding bisphenol A epoxy resin, aminosilane modified dimer acid modified epoxy resin, aminosilane modified 1, 6-hexanediol diglycidyl ether, a dispersing agent, a leveling agent and a defoaming agent into a dispersing cylinder under low-speed stirring at 300-700 rpm, and dispersing for 5-10 min at low speed at 300-700 rpm;
adding sericite powder, filler and aluminum tripolyphosphate, and dispersing at high speed at 1000-1500 rpm until the fineness is less than or equal to 80 mu m;
adding the modified hollow microsphere-flaky aluminum powder slurry composite material and a solvent, and dispersing for 10-15 min at a low speed at 300-700 rpm;
adding thixotropic agent, and dispersing at high speed for 10-15 min at 1000-1500 rpm after the temperature reaches 55-65 ℃;
filtering and packaging to obtain the component A;
the preparation method of the component B comprises the following steps:
adding the curing agent into a dispersing cylinder under low-speed stirring at 50-100 rpm, dispersing for 5-10 min at 500-700 rpm, filtering and packaging to obtain the component B.
In some embodiments, after the preparation of the component A and the component B is completed, the components A and the component B are uniformly mixed according to the mass ratio of (8-11): 1 before the components A and the components B are used.
Based on the above, compared with the prior art, the invention has the following beneficial effects:
1. according to the lightweight high-solid epoxy heavy-duty anticorrosive coating provided by the invention, the lightweight hollow microspheres, the low-density filler, the cathode stripping inhibition filler aluminum powder slurry, the multilayer high-efficiency shielding and the mode of constructing a collaborative design by chemical bonds between a substrate and a coating interface are adopted, so that the coating density is reduced, the thickness of the coating is reduced, the coating is lightweight, and the coating is ensured to have excellent cathode stripping resistance under the lightweight condition.
2. According to the lightweight high-solid epoxy heavy-duty anticorrosive paint provided by the invention, the hollow microsphere-aluminum powder slurry composite material is obtained through modification, so that the compatibility and the dispersibility of the lightweight filler in an epoxy system are improved, the coating density is effectively reduced, and the coating corrosion resistance is improved.
The main component of the hollow microsphere material is SiO 2 And Al 2 O 3 It is light (bulk density of about 0.3-0.4 g/cm) 3 ) The coating density can be effectively reduced, but the coating has strong inorganic characteristics, has large difference with the solubility parameter of an epoxy system, has light weight, and is not ideal in direct mass use and dispersion effect. Most of modified hollow microsphere products on the market at present are research products in colleges and universities, and are subjected to high-temperature treatment at 500-600 ℃, so that the cost is high, and industrialization is not easy to realize.
The heavy anti-corrosion epoxy paint applied to the splash zone and the underwater zone has good cathode stripping resistance, and a large amount of OH-generated in the cathode reaction process can damage the chemical structure of a coating film forming matter, and can generate chemical adsorption competition with the coating at the interface of a substrate to cause the coating to fail. The cathodic disbondment is a weak link of the coating and is prone to failure under reduced thickness conditions.
The flaky aluminum powder slurry can be chemically reacted with a cathode reaction product OH < - >, the concentration of the OH < - >, at the interface, is reduced, the destructiveness of the OH < - > onthe coating is reduced, the competitive adsorption effect of the OH < - > -on the coating is weakened, the cathode stripping resistance of the coating is improved, and meanwhile, A l (OH) generated by the reaction of aluminum powder and the OH < - > -at the later stage is also obtained 3 A l 2 O 3 The deposition can form a layer of compact barrier film on the surface of the substrate, prevent and delay the damage of OH-, C l-and the like, and improve the cathode stripping resistance of the coating under the condition of reduced thickness, so that the good dispersibility is important
The amino silane modified hollow microsphere-aluminum powder slurry technology for the lightweight high-solid epoxy heavy anti-corrosion coating provided by the invention not only improves the dispersibility and compatibility of the hollow microsphere, but also improves the dispersing effect of the aluminum powder slurry and the crosslinking density of the coating, and further improves the cathode stripping resistance of the coating under the film condition. The aluminum powder slurry is a mature pretreatment product, and the surface of the aluminum powder slurry is wrapped with a certain chemical group.
According to the invention, KH560 is hydrolyzed to form Si-OH, S i-OH is utilized to modify aluminum powder slurry to wrap the surface of the aluminum powder slurry and form Si-OH groups, and then the aluminum powder-hollow microsphere composite material is formed by using chemical bonding and physical bonding actions of Si-OH and S i-O, si-OH in hollow microsphere components, so that the compatibility and dispersibility of hollow glass microspheres are improved; meanwhile, the compatibility of epoxy groups and epoxy resin in the modified composite material and the reactivity of a curing agent are utilized to uniformly disperse the modified composite material in a system and finally form a film with the system, so that an aluminum powder sheet-hollow microsphere-aluminum powder sheet good dispersion effect is formed, the modified material is grafted in a crosslinked network structure, the hollow microsphere is light in weight, excellent in corrosion resistance and cathode stripping resistance of aluminum paste are effectively exerted, the crosslinking density of a coating system is improved, and the light weight, heavy corrosion resistance and cathode stripping resistance technology of the whole coating system are realized. The whole modification technology is at 30-50 ℃, only the soaking and high-speed dispersing technology is used, and the preparation is easy to realize in the production and preparation of the coating.
3. According to the lightweight high-solid epoxy heavy-duty anticorrosive coating provided by the invention, through the construction effect of the interface chemical bond, the cathode stripping resistance and the corrosion resistance of the coating are improved, and the lightweight target of the coating is realized.
Adhesion strength is a key factor affecting corrosion resistance of the coating, and corrosive medium H in the corrosion process 2 O, C l-and the like can have competitive adsorption effect with the coating at the interface, the adhesion strength is low, and the corrosion resistance of the coating is poor. OH-with strong damage effect is also generated in the cathode corrosion process, and the adhesion strength requirement on the coating is higher.
The light-weight high-solid epoxy heavy-duty anticorrosive paint provided by the invention is prepared by introducing a silane coupling agent into resin through the reaction of the epoxy resin and amino groups by using silane modified epoxy resin, and preparing the epoxy resin with end groups of epoxy groups and silicon hydroxyl groups (Si-OH) respectively. Besides the hydrogen bonding effect, the silicon hydroxyl in the resin and the silicon hydroxyl in the substrate can also form chemical bonds through the shrinking effect, the interfacial adhesion strength of the common physical doped silane coupling agent coating and the substrate is constructed into chemical bonds through Van der Waals force bonding, the adhesion strength of the coating and the substrate is greatly improved, meanwhile, the other end of the resin reacts with a curing agent to form a film to enable the silane coupling agent to be chemically bonded in a film forming matter system, the negative influence caused by small molecule migration is avoided, the crosslinking density of the coating is not reduced, the corrosion resistance of the coating is improved, and the coating is ensured to have excellent corrosion resistance under the condition of thickness reduction.
Additional features and advantages of the invention will be set forth in the description which follows, and in part will be obvious from the description, or may be learned by practice of the invention. The objectives and other advantages of the invention may be realized and attained by the structure and/or components pointed out in the written description and claims.
Detailed Description
For the purpose of making the objects, technical solutions and advantages of the embodiments of the present invention more apparent, the following description will be made in conjunction with the technical solutions in the embodiments of the present invention, and it is apparent that the described embodiments are some, but not all, embodiments of the present invention; the technical features designed in the different embodiments of the invention described below can be combined with each other as long as they do not conflict with each other; all other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
In the description of the present invention, it should be noted that all terms used in the present invention (including technical terms and scientific terms) have the same meaning as commonly understood by one of ordinary skill in the art to which the present invention belongs and are not to be construed as limiting the present invention; it will be further understood that terms used herein should be interpreted as having a meaning that is consistent with their meaning in the context of this specification and the relevant art and will not be interpreted in an idealized or overly formal sense unless expressly so defined herein.
Examples of the invention are shown in Table 1.
Table 1 example composition ratios
Example 1
The bisphenol A epoxy resin is E51, the dispersing agent is BYK-110, the leveling agent is BYK-354, the defoaming agent is BYK-A530, the filler is 325-mesh talcum powder and 800-mesh wollastonite powder, the mass ratio is 2:1, the solvent is a mixed solvent of dimethylbenzene and n-butyl alcohol of 7:3, and the rheological agent is polyamide wax.
Example 2
The bisphenol A epoxy resin is E51, the dispersing agent is UKa 710S, the leveling agent is UKa 384S, the defoaming agent is UKa 272S, the filler is 325-mesh talcum powder and 800-mesh wollastonite powder, the mass ratio is 1:1, the solvent is a mixed solvent of dimethylbenzene and n-butyl alcohol of 7:3, and the rheological agent is polyamide wax.
Example 3
The bisphenol A epoxy resin is E51, the dispersing agent is UKa 710S, the leveling agent is BYK-320, the defoaming agent is UKa 272S, the filler is 325 mesh talcum powder, the solvent is a mixed solvent of dimethylbenzene and n-butyl alcohol in a ratio of 7:3, and the rheological agent is bentonite and polyamide wax.
Example 4
The bisphenol A epoxy resin is E51, the dispersing agent is UKa 710S, the leveling agent is BYK-320, the defoaming agent is BYK-320, and the filler is 325 mesh talcum powder: the mass ratio of the wollastonite powder of 800 meshes is 4:1, the solvent is a mixed solvent of dimethylbenzene and n-butyl alcohol of 7:3, and the rheological agent is polyamide wax.
Specifically, the specific preparation process of the NDAE, NHEH and modified hollow microsphere-flaky aluminum powder slurry composite material is as follows:
the NDAE is prepared by adding 100g EPD-171 and 0.1g K54 into a 250m l four-neck flask equipped with a mechanical stirring device and a condenser, starting mechanical stirring and condensing water, introducing nitrogen for 30min, heating to 55deg.C, dripping 25.0g gamma-aminopropyl trimethoxysilane solution through a constant pressure dropping funnel for 1.0h, and reacting at a constant temperature for 2.0 h.
The NHEH preparation process is that 100g of 1, 6-hexanediol diglycidyl ether, 0.1g of K54 are added into a 250m l four-neck flask provided with a mechanical stirring device and a condenser, the mechanical stirring and the condensed water are started, nitrogen is introduced for 30min, the temperature is raised to 55 ℃, 50.0g of gamma-aminopropyl trimethoxysilane solution is dripped through a constant pressure dropping funnel for 1.0h, and the reaction is carried out for 2.0h at a constant temperature, thus obtaining the NHEH.
The preparation process of the modified hollow microsphere-flaky aluminum powder slurry composite material comprises the following steps:
step a, preparing KH560 solution with the mass fraction of 10% for standby, wherein the solvent is a mixed solvent of absolute ethyl alcohol and deionized water with the volume ratio of 10:1, and the PH of the KH560 solution is adjusted to about 4 by acetic acid (for preparation at present);
and b, placing 100g of commercial aluminum powder slurry into a four-neck flask of 1000m l, starting condensed water, adding 80g of KH560 solution with mass fraction of 10%, and controlling the temperature to be 40 ℃ and dispersing at 2500r/min for 40min at high speed. Adding 500g of absolute ethyl alcohol and 100g of 500-mesh hollow glass beads or floating beads, and continuing to keep the temperature and disperse at a high speed for 40min;
and c, removing absolute ethyl alcohol in the product by suction filtration, washing with deionized water for 3 times, and drying to obtain the modified hollow microsphere-flaky aluminum powder slurry composite material.
Table 2 comparative example composition ratios
Note that: the preparation process of the modified hollow microsphere is different from the preparation process of the modified hollow microsphere-aluminum powder slurry composite material in that aluminum powder slurry is not added; the preparation process of the modified aluminum powder slurry is different from the preparation process of the modified hollow microsphere-aluminum powder slurry composite material in that hollow glass microspheres or floating beads are not added; the curing agents used in comparative examples 1 to 10 were polyether amine curing agents.
It should be noted that the specific parameters or some common reagents in the above embodiments are specific embodiments or preferred embodiments under the concept of the present invention, and are not limited thereto; and can be adaptively adjusted by those skilled in the art within the concept and the protection scope of the invention.
In addition, unless otherwise specified, the starting materials employed may also be commercially available products or prepared by methods conventional in the art.
The components A and B of the example 1 are calculated according to the mass ratio: b=10: 1. the A and B components of example 2 were as defined for A: b=8.6: 1. the A and B components of example 3 were as defined for A: b=10.5: the A and B components of 1 and example 4 are as defined for A: b=9.7: 1 and comparative example 1 a: ethyl=9.8:1, comparative example 2 a: ethyl=9.6:1, comparative example 3 a: b=9.2:1, ratio 4 to 10 according to a: performance testing was performed at b=10:1 and the test results are shown in table 3.
Table 3 results of performance of examples and comparative examples
As can be seen from Table 3, the coating prepared by the lightweight high-solid epoxy heavy-duty anticorrosive coating provided by the invention still has excellent salt spray resistance, cathode stripping resistance, adhesion strength and low surface density when the thickness of the coating is reduced by 160um, the anticorrosive performance of the coating meets the index requirement when the thickness of the coating is 160um (the cathode stripping index is that the single-side stripping width is less than or equal to 8 mm), the surface density is reduced from 0.46Kg/m < 2 > of 320um to 0.35Kg/m < 2 >, the lightweight target of the coating is realized, and the anticorrosive property of the coating is ensured.
From examples 1 to 4 and comparative example 10, the synergistic effect of the modified resin and the hollow microsphere-aluminum powder slurry composite material adopted by the invention effectively improves the corrosion resistance and the cathode stripping resistance of the lightweight high-solid epoxy heavy anti-corrosion coating, effectively reduces the areal density, and successfully realizes the coating lightweight target; from examples 1 to 4 and comparative examples 1 to 3, it can be seen that the aminosilane modified resin technology effectively improves the adhesion strength and corrosion resistance of the coating, and reduces the thickness of the coating; from examples 1 to 4 and comparative examples 4 to 8, it can be seen that the hollow microsphere-aluminum paste composite material can effectively improve the cathode stripping resistance and adhesion strength of the coating, and reduce the coating density, thereby reducing the coating thickness and the coating surface density; from examples 1 to 4 and comparative example 9, it can be seen that the synergistic effect of the platy filler sericite powder, the chemical rust-preventive pigment aluminum tripolyphosphate and other fillers is beneficial to improving the corrosion resistance of the lightweight high-solid epoxy heavy-duty anticorrosive paint.
In conclusion, compared with the prior art, the light-weight high-solid-content epoxy heavy-duty anticorrosive paint provided by the invention has excellent corrosion resistance through the integral synergistic effect of the formula, meets the cathode stripping resistance index under the condition of reducing the thickness of the coating, and achieves the aim of light weight of the coating.
In addition, it should be understood by those skilled in the art that although many problems exist in the prior art, each embodiment or technical solution of the present invention may be modified in only one or several respects, without having to solve all technical problems listed in the prior art or the background art at the same time. Those skilled in the art will understand that nothing in one claim should be taken as a limitation on that claim.
Although terms such as a component a, a component b, etc. are more used herein, the possibility of using other terms is not excluded. These terms are used merely for convenience in describing and explaining the nature of the invention; they are to be interpreted as any additional limitation that is not inconsistent with the spirit of the present invention; the terms first, second, and the like in the description and in the claims, if any, are used for distinguishing between similar elements and not necessarily for describing a particular sequential or chronological order.
Finally, it should be noted that: the above embodiments are only for illustrating the technical solution of the present invention, and not for limiting the same; although the invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical scheme described in the foregoing embodiments can be modified or some or all of the technical features thereof can be replaced by equivalents; such modifications and substitutions do not depart from the spirit of the invention.
Claims (10)
1. A lightweight high-solid epoxy heavy-duty anticorrosive paint is characterized in that:
the raw materials comprise a component A and a component B, wherein the component A comprises the following components in parts by mass
The component B comprises a curing agent;
the mass ratio of the component A to the component B is 8-11:1.
2. The lightweight high solids epoxy heavy duty anticorrosive paint of claim 1, wherein: the epoxy equivalent of the bisphenol A epoxy resin is 180-200g/eq.
3. The lightweight high-solid epoxy heavy-duty anticorrosive paint according to claim 1, wherein the specific modification process of the aminosilane modified dimer acid modified epoxy resin is as follows:
adding 100 parts of dimer acid modified epoxy resin and 0.1 part of K54 into a reaction container in parts by weight, and stirring; then introducing nitrogen for 30min, heating to 50-60 ℃, dropwise adding 25.0 parts of gamma-aminopropyl trimethoxy silane solution for 1.0h, and then carrying out heat preservation reaction for 2.0h to obtain the aminosilane modified dimer acid modified epoxy resin.
4. The lightweight high-solid epoxy heavy-duty anticorrosive paint according to claim 1, wherein the aminosilane modified 1, 6-hexanediol diglycidyl ether is prepared by the following steps:
100 parts of 1, 6-hexanediol diglycidyl ether and 0.1 part of K54 are added into a reaction vessel in parts by mass, stirring is carried out, nitrogen is introduced for 30min, the temperature is raised to 50-60 ℃, 50.0 parts of gamma-aminopropyl trimethoxysilane solution is dropwise added for 1.0h, and then the reaction is carried out for 2.0h in a heat-preserving way, thus obtaining the aminosilane modified 1, 6-hexanediol diglycidyl ether.
5. The lightweight high solids epoxy heavy duty anticorrosive paint of claim 1, wherein: the dispersing agent comprises any one of BYK-110 and UKa 710S; the leveling agent comprises any one of BYK-354 and UKa 384S; the defoamer comprises any one of BYK-A530 and UKa 272S.
6. The lightweight high-solid epoxy heavy-duty anticorrosive paint according to claim 1, wherein the modified hollow microsphere-flaky aluminum paste composite material is modified by the following steps:
100 parts of aluminum powder slurry is placed in a reaction container, 80 parts of KH560 solution with the mass fraction of 10% is added, the temperature is controlled to be 40-45 ℃, and 2500r/min is dispersed for 40min at a high speed; adding 500 parts of absolute ethyl alcohol and 100 parts of 500-mesh hollow glass beads or floating beads, and continuing to keep the temperature and disperse at a high speed for 40min;
and filtering to remove absolute ethyl alcohol in the product, washing with deionized water, and drying to obtain the modified hollow microsphere-flaky aluminum powder slurry composite material.
7. The lightweight high solids epoxy heavy duty anticorrosive paint of claim 1, wherein: the filler is one or more of talcum powder and wollastonite powder.
8. The lightweight high solids epoxy heavy duty anticorrosive paint of claim 1, wherein: the thixotropic agent is polyamide wax.
9. The lightweight high solids epoxy heavy duty anticorrosive paint of claim 1, wherein: the curing agent is any one or combination of polyether amine curing agent, cashew nut shell oil modified amine curing agent and alicyclic amine curing agent.
10. A method for preparing the lightweight high-solid epoxy heavy-duty anticorrosive paint as claimed in any one of claims 1 to 9, which is characterized by comprising the following steps:
the preparation method of the component A comprises the following steps:
adding bisphenol A epoxy resin, aminosilane modified dimer acid modified epoxy resin, aminosilane modified 1, 6-hexanediol diglycidyl ether, a dispersing agent, a leveling agent and a defoaming agent into a dispersing cylinder under low-speed stirring at 300-700 rpm, and dispersing for 5-10 min at low speed at 300-700 rpm;
adding sericite powder, filler and aluminum tripolyphosphate, and dispersing at high speed at 1000-1500 rpm until the fineness is less than or equal to 80 mu m;
adding the modified hollow microsphere-flaky aluminum powder slurry composite material and a solvent, and dispersing for 10-15 min at a low speed at 300-700 rpm;
adding thixotropic agent, and dispersing at high speed for 10-15 min at 1000-1500 rpm after the temperature reaches 55-65 ℃;
filtering and packaging to obtain the component A;
the preparation method of the component B comprises the following steps:
adding the curing agent into a dispersing cylinder under low-speed stirring at 50-100 rpm, dispersing for 5-10 min at 500-700 rpm, filtering and packaging to obtain the component B.
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