CN115141533B - Environment-friendly corrosion-resistant waterborne graphene coating and preparation method thereof - Google Patents
Environment-friendly corrosion-resistant waterborne graphene coating and preparation method thereof Download PDFInfo
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- CN115141533B CN115141533B CN202110996444.5A CN202110996444A CN115141533B CN 115141533 B CN115141533 B CN 115141533B CN 202110996444 A CN202110996444 A CN 202110996444A CN 115141533 B CN115141533 B CN 115141533B
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 71
- 238000000576 coating method Methods 0.000 title claims abstract description 59
- 239000011248 coating agent Substances 0.000 title claims abstract description 58
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 57
- 230000007797 corrosion Effects 0.000 title claims abstract description 35
- 238000005260 corrosion Methods 0.000 title claims abstract description 35
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- 239000000463 material Substances 0.000 claims abstract description 29
- 239000000049 pigment Substances 0.000 claims abstract description 25
- -1 carboxyl modified graphene Chemical class 0.000 claims abstract description 22
- 229920005989 resin Polymers 0.000 claims abstract description 20
- 239000011347 resin Substances 0.000 claims abstract description 20
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 16
- 150000001875 compounds Chemical class 0.000 claims abstract description 15
- 229920000768 polyamine Polymers 0.000 claims abstract description 15
- 239000002994 raw material Substances 0.000 claims abstract description 7
- 239000002904 solvent Substances 0.000 claims abstract description 5
- 239000003822 epoxy resin Substances 0.000 claims description 54
- 229920000647 polyepoxide Polymers 0.000 claims description 54
- 239000013530 defoamer Substances 0.000 claims description 27
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 26
- 239000002562 thickening agent Substances 0.000 claims description 21
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 20
- 235000019832 sodium triphosphate Nutrition 0.000 claims description 17
- 239000002356 single layer Substances 0.000 claims description 16
- 238000003756 stirring Methods 0.000 claims description 16
- 238000000034 method Methods 0.000 claims description 15
- 230000008569 process Effects 0.000 claims description 12
- LRXTYHSAJDENHV-UHFFFAOYSA-H zinc phosphate Chemical compound [Zn+2].[Zn+2].[Zn+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O LRXTYHSAJDENHV-UHFFFAOYSA-H 0.000 claims description 11
- 229910000165 zinc phosphate Inorganic materials 0.000 claims description 11
- 229920002401 polyacrylamide Polymers 0.000 claims description 5
- 150000001412 amines Chemical class 0.000 claims description 4
- 239000002518 antifoaming agent Substances 0.000 claims description 4
- 238000007599 discharging Methods 0.000 claims description 4
- 238000001914 filtration Methods 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 4
- 239000003973 paint Substances 0.000 abstract description 20
- 239000000758 substrate Substances 0.000 abstract description 11
- 239000000853 adhesive Substances 0.000 abstract description 7
- 230000001070 adhesive effect Effects 0.000 abstract description 7
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 abstract description 5
- 230000006750 UV protection Effects 0.000 abstract description 3
- 241000237858 Gastropoda Species 0.000 abstract description 2
- 230000008859 change Effects 0.000 abstract description 2
- 239000002585 base Substances 0.000 description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 15
- 230000000694 effects Effects 0.000 description 8
- UNXRWKVEANCORM-UHFFFAOYSA-I triphosphate(5-) Chemical compound [O-]P([O-])(=O)OP([O-])(=O)OP([O-])([O-])=O UNXRWKVEANCORM-UHFFFAOYSA-I 0.000 description 8
- 239000000178 monomer Substances 0.000 description 6
- 229910052782 aluminium Inorganic materials 0.000 description 5
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 5
- 238000005336 cracking Methods 0.000 description 5
- 238000002474 experimental method Methods 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 230000005856 abnormality Effects 0.000 description 4
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- 239000007921 spray Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 239000003513 alkali Substances 0.000 description 3
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical group [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 3
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 239000007769 metal material Substances 0.000 description 3
- 239000002086 nanomaterial Substances 0.000 description 3
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
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- 238000006243 chemical reaction Methods 0.000 description 2
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- 229910052802 copper Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- XXBDWLFCJWSEKW-UHFFFAOYSA-N dimethylbenzylamine Chemical class CN(C)CC1=CC=CC=C1 XXBDWLFCJWSEKW-UHFFFAOYSA-N 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 230000004224 protection Effects 0.000 description 2
- DNIAPMSPPWPWGF-GSVOUGTGSA-N (R)-(-)-Propylene glycol Chemical compound C[C@@H](O)CO DNIAPMSPPWPWGF-GSVOUGTGSA-N 0.000 description 1
- JDSQBDGCMUXRBM-UHFFFAOYSA-N 2-[2-(2-butoxypropoxy)propoxy]propan-1-ol Chemical compound CCCCOC(C)COC(C)COC(C)CO JDSQBDGCMUXRBM-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 1
- 229910001200 Ferrotitanium Inorganic materials 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 159000000021 acetate salts Chemical class 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- BIOOACNPATUQFW-UHFFFAOYSA-N calcium;dioxido(dioxo)molybdenum Chemical compound [Ca+2].[O-][Mo]([O-])(=O)=O BIOOACNPATUQFW-UHFFFAOYSA-N 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 238000004210 cathodic protection Methods 0.000 description 1
- 239000008199 coating composition Substances 0.000 description 1
- 239000011247 coating layer Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 238000005536 corrosion prevention Methods 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 238000005034 decoration Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000004925 denaturation Methods 0.000 description 1
- 230000036425 denaturation Effects 0.000 description 1
- 238000002845 discoloration Methods 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 229920000587 hyperbranched polymer Polymers 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 239000010445 mica Substances 0.000 description 1
- 229910052618 mica group Inorganic materials 0.000 description 1
- 239000003595 mist Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 238000002715 modification method Methods 0.000 description 1
- 229910052755 nonmetal Inorganic materials 0.000 description 1
- 238000002161 passivation Methods 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000007665 sagging Methods 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- PXQLVRUNWNTZOS-UHFFFAOYSA-N sulfanyl Chemical class [SH] PXQLVRUNWNTZOS-UHFFFAOYSA-N 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
- 238000004383 yellowing Methods 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
- 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
- C09D5/082—Anti-corrosive paints characterised by the anti-corrosive pigment
- C09D5/084—Inorganic 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
- C09D7/20—Diluents or solvents
-
- 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
- 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
- C08K3/32—Phosphorus-containing compounds
- C08K2003/321—Phosphates
- C08K2003/327—Aluminium phosphate
-
- 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
- C08K3/32—Phosphorus-containing compounds
- C08K2003/321—Phosphates
- C08K2003/328—Phosphates of heavy metals
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 discloses an environment-friendly corrosion-resistant waterborne graphene coating, which comprises the following preparation raw materials in percentage by weight: 15-35% of resin base material, 20-40% of pigment, 0.01-0.5% of graphene, 5-18% of auxiliary agent, 5-15% of organic polyamine compound and the balance of solvent. According to the environment-friendly corrosion-resistant aqueous graphene coating, the carboxyl modified graphene is adopted, so that the adhesive force between the coating and a substrate can be improved, and the mechanical property and the corrosion resistance of the coating are improved; the stability of the product can be improved, the base material coated by the paint is not easy to rust, the paint is not easy to fall off, snail lines are not easy to generate, the paint has good stability, and meanwhile, the corrosion resistance, the tolerance, the ultraviolet resistance and the weather change resistance of the paint are further improved, so that the paint is particularly suitable for base materials with severe requirements on environment, such as vehicles, tracks and the like.
Description
Technical Field
The invention relates to an environment-friendly corrosion-resistant waterborne graphene coating and a preparation method thereof, and relates to C09D, in particular to the field of coating compositions.
Background
The metallic material is easy to generate corrosion reaction with oxygen and water in the environment, so that the normal use of the metallic material is influenced, a large amount of metallic material is wasted each year because of corrosion, the occurrence of the corrosion reaction can be greatly reduced by coating the coating material on the surface of the metal, but the coating on the market at present is poor in mechanical property and poor in stability, and the corrosion prevention effect is difficult to be exerted for a long time. And the bonding adhesive force between the paint and the base material, especially the metal steel is poor, the paint is easy to fall off in the use process, the protection time is not long, the ultraviolet resistance and the weather resistance are not strong, the problems of color change and denaturation are easy to occur, and the service life is shorter in the outdoor environment. The environment-friendly corrosion-resistant aqueous graphene coating disclosed by the invention has good adhesion with a metal substrate, also has good mechanical strength and weather resistance, and can simultaneously meet the effects of protection and decoration.
Chinese patent No. 200710025173.9 discloses an environment-friendly normal-temperature-curing water-based epoxy resin coating, which reduces the toxicity of the coating and improves the environment-friendly effect by using lower aliphatic alcohol instead of propylene glycol ether, but the prepared water-based epoxy resin coating has low water resistance and is easy to generate the problems of foaming and falling after being soaked in water for a long time. Chinese patent No. cn201610515546.X discloses an anticorrosive aqueous epoxy resin composition having excellent anticorrosive effect, but the use process requires multilayer coating of the composition, which is complicated and takes a long time.
Disclosure of Invention
In order to improve weather resistance and corrosion resistance of the water-based paint, the first aspect of the invention provides an environment-friendly corrosion-resistant water-based graphene paint, which is prepared from the following raw materials in percentage by weight: 15-35% of resin base material, 20-40% of pigment, 0.01-0.5% of graphene, 5-18% of auxiliary agent, 5-15% of organic polyamine compound and the balance of solvent.
As a preferred embodiment, the resin base is a modified epoxy resin, and the modified epoxy resin is selected from one or a combination of several of polysiloxane modified epoxy resin, hyperbranched polymer modified epoxy resin, acrylic modified epoxy resin, polyamide modified epoxy resin, polyester modified epoxy resin, nano metal oxide modified epoxy resin and nano nonmetal modified epoxy resin.
As a preferred embodiment, the modified epoxy resin is an acrylic modified epoxy resin.
As a preferred embodiment, the weight ratio of acrylic acid to epoxy resin in the acrylic modified epoxy resin is 1: (0.75-1.25).
As a preferred embodiment, the weight ratio of acrylic acid to epoxy resin in the acrylic modified epoxy resin is 1: (0.75-1).
Further preferably, the weight ratio of acrylic acid to epoxy resin in the acrylic acid modified epoxy resin is 1:0.85.
as a preferred embodiment, the modified epoxy resin has a viscosity of 1400-2200mPa.s at 25 ℃.
As a preferred embodiment, the viscosity of the modified epoxy resin is 1400-2000mpa.s at 25 ℃.
Further preferably, the viscosity of the modified epoxy resin is 190 mpa.s at 25 ℃.
The applicant found during the experiment that when the weight ratio of acrylate to epoxy resin is 1: (0.75-1), the paint can have proper viscosity, which is beneficial to improving the adhesive force between the paint and the substrate, and the paint also has better stability, and the phenomena such as layering precipitation and the like can not occur, and the possible reasons are hypothesized to be: when the weight ratio of the acrylic ester to the epoxy resin is 1: (0.75-1), the acrylic acid monomer can be uniformly dispersed among the epoxy resin to form emulsion particle size with proper size, so that the copolymerization trend among the monomers caused by excessive acrylic acid monomer is avoided, the formation of linear acrylic ester copolymer is reduced, the coating has proper viscosity, and good adhesive force with a substrate can be realized. And because the acrylic acid monomer is uniformly dispersed in the epoxy resin, the acrylic acid and the epoxy resin have good compatibility, the formed coating has good stability, and the phenomenon of layering precipitation can not occur. When hydrophilic groups in the acrylic acid monomer are connected to the main chain of the epoxy resin, the hydrophilicity of the resin base material can be improved, polar groups on a polymer molecular chain are increased, more active sites can be provided, the adhesive force is improved, the crosslinking density of the polymer can be improved, and the corrosion resistance of the coating is improved, but if the acrylic acid monomer is excessively introduced, the water absorption rate of the coating is increased, and the adhesive force is reduced.
As a preferred embodiment, the pigment is selected from one or a combination of several of zinc phosphate, mica iron oxide, aluminum tripolyphosphate, molybdate, calcium iron powder, ferrotitanium powder and derivatives thereof.
As a preferred embodiment, the pigment is a combination of aluminum tripolyphosphate and zinc phosphate.
As a preferred embodiment, the aluminum tripolyphosphate is a modified aluminum tripolyphosphate.
As a preferred embodiment, the weight ratio of the modified aluminum tripolyphosphate to the zinc phosphate is 1: (1-5).
As a preferred embodiment, the weight ratio of the modified aluminum tripolyphosphate to the zinc phosphate is 1: (1-3).
As a preferred embodiment, the weight ratio of the modified aluminum tripolyphosphate to the zinc phosphate is 1:2.
as a preferred embodiment, the pigment comprises 20-40% of the total weight fraction of the coating.
As a preferred embodiment, the pigment comprises 25 to 35% by weight of the total weight of the coating.
Further preferably, the pigment comprises 30% of the total weight fraction of the coating.
The applicant found during the experiment that the pigment selected a combination of aluminium tripolyphosphate and zinc phosphate, and the weight ratio was 1: (1-3) can improve the corrosion resistance and the tolerance of the paint, and the possible reasons are suspected to be: the aluminum tripolyphosphate can have good chelating force with zinc ions in zinc phosphate, a thicker passivation film is formed on the surface of a coated substrate, the corrosion of an iron substrate is well inhibited, the modified aluminum tripolyphosphate contains a double bond conjugated structure, good adhesive force can be generated with the substrate, and the capability of transferring electrons is improved due to the conjugated structure, so that the effect of cathodic protection is enhanced. The hardness of the coating can be increased when the pigment is 30% by weight of the total coating weight, and also does not cause a decrease in the resistance, presumably because: when the pigment accounts for 30 percent of the total weight of the paint, the epoxy resin can fully cover the surface of the pigment, the blocking effect on the coating is enhanced, and the paint has better corrosion resistance and tolerance.
As a preferred embodiment, the graphene is modified graphene, and the modified graphene is selected from one of graphene oxide, nitrogen-doped graphene, carboxylated graphene, mercapto graphene, and imidazole graphite.
As a preferred embodiment, the modified graphene is carboxylated graphene.
As a preferred embodiment, the monolayer ratio of the modified graphene is 80-90%, and the monolayer thickness is 0.8-1.2nm.
As a preferred embodiment, the monolayer ratio of the modified graphene is 80-85%, and the monolayer thickness is 0.9-1.1nm.
As a preferred embodiment, the monolayer ratio of the modified graphene is 83% and the monolayer thickness is 1nm.
As a preferred embodiment, the modified graphene has a sheet diameter of 200 to 500nm.
As a preferred embodiment, the modified graphene has a sheet diameter of 300nm.
As a preferred embodiment, the modification method of the modified graphene is surface modification.
The applicant finds that the tensile strength and the compressive strength of the coating can be improved by adding carboxyl modified graphene in the experimental process, the mechanical property is greatly improved, and the possible reasons are hypothesized to be: the modified graphene introduces carboxyl, hydroxyl and oxygen-containing groups on the surface of graphene, so that interface interaction between the carboxylated graphene and epoxy resin can be improved, after the resin is cured, the carboxylated graphene can be uniformly distributed in the epoxy resin, when the composite material is subjected to external force, cracks on the surface of the carboxylated graphene can absorb external energy, so that the mechanical impact of external force on the coating is weakened, the single-layer rate is 80-85%, and the carboxylated graphene with the single-layer thickness of 0.8-1.2nm can disperse the impact force into adjacent sheets, so that larger external force load can be borne, and the mechanical strength of the coating is improved. And carboxylated graphene with the sheet diameter of 200-500nm can be uniformly dispersed in the epoxy resin, so that the reduction of mechanical strength caused by agglomeration of the carboxylated graphene in the epoxy resin is avoided.
As a preferred embodiment, the weight ratio of the resin base material to the modified graphene is 1: (0.01-0.05).
As a preferred embodiment, the weight ratio of the resin base material to the modified graphene is 1: (0.02-0.04).
As a preferred embodiment, the weight ratio of the resin base material to the modified graphene is 1:0.03.
the applicant finds in the experimental process that the weight ratio of the modified epoxy resin to the carboxyl modified graphene is 1: the coating prepared at (0.02-0.04) has excellent mechanical strength, and the possible reasons are suspected to be: the weight ratio of the modified epoxy resin to the carboxyl modified graphene is 1: and (0.02-0.04), carboxyl modified graphene can be uniformly dispersed in modified epoxy resin, so that the modified epoxy resin-based paint can bear external pressure in all aspects, and the external pressure is dispersed, so that larger mechanical pressure can be borne. However, when the weight ratio is out of the preferred range, the carboxyl modified graphene is agglomerated, mechanical defects are formed in the epoxy resin system, and the mechanical strength of the coating is reduced.
As a preferred embodiment, the auxiliary agent is selected from at least two of a dispersant, a leveling agent, a defoamer, an anti-yellowing agent, and a thickener.
As a preferred embodiment, the auxiliary agent includes an antifoaming agent and a thickening agent.
As a preferred embodiment, the weight ratio of the defoamer to the thickener is 1: (0.3-0.8).
As a preferred embodiment, the weight ratio of the defoamer to the thickener is 1:0.6.
as a preferred embodiment, the defoamer is a combination of a silicon-type defoamer and a polymeric-type defoamer.
As a preferred embodiment, the defoamers are the FoamStar ST defoamer and the flunine 7610 type defoamer.
As a preferred embodiment, the weight ratio of FoamStar ST defoamer to the Dow Corning 7610 type defoamer is 1 (1-4).
As a preferred embodiment, the weight ratio of the FoamStar ST defoamer to the form 7610 defoamer of the dakaning is 1:1.5.
the applicant found in the experimental process that the combination of the FoamStar ST defoamer and the dakangnin 7610 defoamer can make the paint have good leveling effect, have good wetting effect on the substrate in the coating process of the paint, and have firm adhesion between the paint and the substrate. And when the two defoamers are combined, quick defoaming can be realized, and the formed coating is flat and has no shrinkage cavity.
As a preferred embodiment, the thickener is one selected from the group consisting of cellulose-based thickeners, polyacrylate-based thickeners, and polyurethane-based thickeners.
As a preferred embodiment, the thickener is a nonionic polyacrylamide thickener, and the applicant has found during experiments that the nonionic polyacrylamide thickener can form a special network structure among the epoxy resin, pigment particles and organic polyamine compound, so that the viscosity is increased, and the paint has better storage stability and sagging prevention effect through the preferred thickener.
As a preferred embodiment, the organic polyamine compound is selected from one of polyetheramine, polyacrylamide, phenolic modified amine, N-dimethylbenzylamine.
As a preferred embodiment, the organic polyamine compound is phenolic modified amine, and the applicant finds that the phenolic modified amine compound has higher reactivity with epoxy resin in the experimental process, can realize curing in a low-temperature and humid environment, and can reach a proper curing speed, so that the internal curing time is nearly consistent with the surface curing time, and a coating layer with stable performance is formed.
The second aspect of the invention provides a preparation method of an environment-friendly corrosion-resistant waterborne graphene coating, which comprises the following steps:
(1) Stirring the resin base material at a rotating speed of 1000-1500r/min, and adding an auxiliary agent and a solvent in the stirring process;
(2) Continuously stirring, adding graphene, pigment and organic polyamine compound, mixing and stirring for 20-40min;
(3) Filtering and discharging the mixture to obtain the product.
Compared with the prior art, the invention has the following beneficial effects:
(1) According to the environment-friendly corrosion-resistant waterborne graphene coating disclosed by the invention, through optimizing a proper modified epoxy resin base material, the coating can reach proper viscosity, and the phenomena of dripping and hanging and nozzle blocking are reduced during construction operation.
(2) According to the environment-friendly corrosion-resistant waterborne graphene coating disclosed by the invention, the adhesion between the coating and a substrate can be improved and the mechanical property and the corrosion resistance of the coating can be improved by optimizing the carboxyl modified graphene with the monolayer rate of 80-85% and the monolayer thickness of 0.8-1.2nm.
(3) According to the environment-friendly corrosion-resistant aqueous graphene coating disclosed by the invention, the weight ratio of the acrylic acid modified epoxy resin to the carboxyl modified graphene is optimized, so that the stability of a product can be improved, a substrate coated by the coating is not easy to rust, the coating is not easy to fall off, snail lines are not easy to generate, and the product has good stability.
(4) According to the environment-friendly corrosion-resistant aqueous graphene coating, the combination of the modified aluminum tripolyphosphate and the zinc phosphate is adopted as the pigment, and the mass ratio of the proper pigment in the whole coating is selected, so that the corrosion resistance, the tolerance, the ultraviolet resistance and the weather resistance of the coating are further improved, and the environment-friendly corrosion-resistant aqueous graphene coating is particularly suitable for base materials with severe requirements on environment, such as vehicles, tracks and the like.
(5) The environment-friendly corrosion-resistant aqueous graphene coating disclosed by the invention is easy to obtain in raw materials, simple and convenient in process and strong in practicability, contains few volatile substances, is environment-friendly and pollution-free in preparation and use processes, and has a wide application prospect.
Detailed Description
The present invention will be specifically described below by way of examples. It is noted herein that the following examples are given solely for the purpose of further illustration and are not to be construed as limitations on the scope of the invention, as will be apparent to those skilled in the art in light of the foregoing disclosure.
In addition, the raw materials used are commercially available unless otherwise indicated.
Example 1
The environment-friendly corrosion-resistant aqueous graphene coating comprises the following preparation raw materials in percentage by weight: 30% of resin base material, 30% of pigment, 0.09% of graphene, 15% of auxiliary agent, 10% of organic polyamine compound and the balance of water.
The resin base material is acrylic acid modified epoxy resin, and the weight ratio of acrylic acid to epoxy resin is 1:0.85, viscosity at 25℃of 190 mPa.s, and acrylic modified epoxy resin was purchased from Wuhanshiquanxing New Material technologies Co., ltd.
The pigment is modified aluminum tripolyphosphate and zinc phosphate, and the weight ratio is 1:2, the modified aluminum tripolyphosphate was purchased from Hubei's United pharmaceutical Co.
The graphene is carboxylated graphene, the single-layer rate is 83%, the single-layer thickness is 1nm, the sheet diameter is 300nm, and the graphene is purchased from Nanjing Xianfeng nano material technology Co.
The auxiliary agent is a defoaming agent and a thickening agent, and the weight ratio is 1:0.6.
the defoamer is a combination of a FoamStar ST defoamer and a dakangnin 7610 defoamer, and the weight ratio is 1:1.5 FoamStar ST defoamer was purchased from Basoff, dow Corning 7610 defoamer was purchased from Dongguan City, inc. of New materials.
The thickener is a nonionic polyacrylamide thickener, and is purchased from Shanghai Kailn chemical Co.
The organic polyamine compound is phenolic aldehyde modified amine, and is purchased from Jinan Linhai chemical industry Co.
The preparation method of the environment-friendly corrosion-resistant aqueous graphene coating comprises the following steps:
(1) Stirring the resin base material at a rotating speed of 1500r/min, and adding an auxiliary agent, water and the auxiliary agent in the stirring process;
(2) Continuing stirring, adding graphene, and mixing and stirring the pigment and the organic polyamine compound for 30min;
(3) Filtering and discharging the mixture to obtain the product.
Example 2
The environment-friendly corrosion-resistant aqueous graphene coating comprises the following preparation raw materials in percentage by weight: 35% of resin base material, 25% of pigment, 0.1% of graphene, 13% of auxiliary agent, 8% of organic polyamine compound and the balance of water.
The resin base material is acrylic acid modified epoxy resin, and the weight ratio of acrylic acid to epoxy resin is 1:0.75, viscosity at 25 ℃ of 2000mpa.s, available from new materials science and technology Co., ltd.
The pigment is modified aluminum tripolyphosphate and zinc phosphate, and the weight ratio is 1:1, the modified aluminum tripolyphosphate was purchased from Hubei's United pharmaceutical Co.
The graphene is carboxylated graphene, the single-layer rate is 80%, the single-layer thickness is 1.1nm, the sheet diameter is 400nm, and the graphene is purchased from Nanjing Xianfeng nano material technology Co.
The auxiliary agent is a defoaming agent and a thickening agent, and the weight ratio is 1:0.5.
the defoamer is a combination of a FoamStar ST defoamer and a dakangnin 7610 defoamer, and the weight ratio is 1:1.5 FoamStar ST defoamer was purchased from Basoff, dow Corning 7610 defoamer was purchased from Dongguan City, inc. of New materials.
The thickener is cellulose thickener, and is purchased from chemical industry limited company of Dacheng county.
The organic polyamine compound is N, N-dimethylbenzylamine, which is purchased from Hubei Tosoh chemical technology Co., ltd.
The preparation method of the environment-friendly corrosion-resistant aqueous graphene coating comprises the following steps:
(1) Stirring the resin base material at the rotating speed of 1300r/min, and adding the auxiliary agent, water and the auxiliary agent in the stirring process;
(2) Continuing stirring, adding graphene, and mixing and stirring the pigment and the organic polyamine compound for 40min;
(3) Filtering and discharging the mixture to obtain the product.
Example 3
The preparation method of the environment-friendly corrosion-resistant waterborne graphene coating comprises the following specific steps that the specific steps are the same as those in the embodiment 1, and the difference is that the resin base material is acrylic acid modified epoxy resin, and the weight ratio of acrylic acid to epoxy resin is 1:0.6, acrylic modified epoxy resin was purchased from Wuhanshiquanxing New Material technologies Co., ltd.
Example 4
An environment-friendly corrosion-resistant waterborne graphene coating and a preparation method thereof are provided, and the specific steps are the same as those of example 1, except that the carboxylated graphene has a sheet diameter of 650nm and is purchased from Nanjing Xianfeng nanomaterial technologies, inc.
Example 5
An environment-friendly corrosion-resistant aqueous graphene coating and a preparation method thereof are provided, and the specific steps are the same as those of the embodiment 1, except that the pigment is modified aluminum tripolyphosphate.
Performance test:
1. and (3) water resistance test: examples 1 to 5 were tested for water resistance according to GB/T1733-1993, and the results are shown in Table 1, in which no phenomena of foaming, flaking, rust and cracking occurred for a long period of time.
2. Acid resistance test: the acid resistance of example 1 was measured in 50g/L sulfuric acid solution according to the method A of GB/T9274-1988 standard and the results are shown in Table 2.
3. Alkali resistance test: the alkali resistance of example 1 was measured in 50g/L sodium hydroxide solution according to the medium A method of GB/T9274-1988 standard and the results are shown in Table 2.
4. Wet heat resistance: examples 1 to 5 were tested for wet heat resistance according to GB/T1740-2007, and the results are shown in Table 1, showing no occurrence of phenomena of foaming, flaking, rust and cracking.
5. Salt spray resistance: examples 1 to 5 were tested for salt spray resistance according to GB/T1771-2007 standard, the coating thickness was 100.+ -.10. Mu.m, and the test time was long enough to avoid the occurrence of bubbling, flaking, rusting, cracking, and the results are shown in Table 1.
6. High temperature resistance: the coating variation of example 1 was tested according to the GB/T1735-2009 standard at 70℃for 48h, the results are shown in Table 2.
7. Low temperature resistance: the coating variation of example 1 was tested at-40℃for 48 hours according to GB/T9268-2008 standard and the results are shown in Table 2.
8. Copper accelerated acetate fog experiment: the acetate mist resistance of example 1 was tested according to the GB/T10125-2012 standard, the coating thickness being 100.+ -.10. Mu.m, and the results being shown in Table 2.
9. Resistance to weathering: the artificial weathering resistance of example 1 was tested according to GB/T1865-2009 standard and the results are shown in Table 2.
TABLE 1
| Water resistance/h | Moisture and heat resistance/h | Salt spray resistance/h | |
| Example 1 | ＞2500 | ＞1750 | ＞5000 |
| Examples2 | 2470-2500 | 1730-1750 | 4950-5000 |
| Example 3 | 2100-2200 | 1650-1660 | 4850-4860 |
| Example 4 | 2200-2300 | 1660-1670 | 4840-4850 |
| Example 5 | 2000-2100 | 1670-1680 | 4860-4870 |
TABLE 2
| Acid resistance | 192h without abnormality |
| Alkali resistance | 2500h without abnormality |
| High temperature resistance | No abnormality |
| Low temperature resistanceCan be used for | No abnormality |
| Copper accelerated acetate salt spray experiment | No phenomena of bubbling, peeling, rust and cracking exist in 800 hours |
| Resistance to artificial weathering | No foaming, peeling and cracking phenomenon, 0 grade pulverization and 0 grade discoloration after 2000 hours |
Claims (2)
1. The environment-friendly corrosion-resistant aqueous graphene coating is characterized by comprising the following preparation raw materials in percentage by weight: 15-35% of resin base material, 20-40% of pigment, 0.01-0.5% of graphene, 5-18% of auxiliary agent, 5-15% of organic polyamine compound and the balance of solvent;
the resin base material is acrylic acid modified epoxy resin, and the weight ratio of acrylic acid to epoxy resin in the acrylic acid modified epoxy resin is 1:0.85, a viscosity of 1900mPa.s at 25 ℃;
the graphene is carboxylated graphene, the single-layer rate of the carboxylated graphene is 83%, the single-layer thickness is 1nm, and the sheet diameter of the carboxylated graphene is 300nm;
the pigment is a combination of modified aluminum tripolyphosphate and zinc phosphate, and the weight ratio is 1:2;
the weight ratio of the resin base material to the graphene is 1:0.03;
the auxiliary agent is a defoaming agent and a thickening agent, and the weight ratio is 1:0.6; the defoamer is a combination of a FoamStar ST defoamer and a dakangnin 7610 defoamer, and the weight ratio is 1:1.5; the thickener is nonionic polyacrylamide thickener;
the organic polyamine compound is phenolic aldehyde modified amine.
2. A method for preparing the environment-friendly corrosion-resistant aqueous graphene coating according to claim 1, which is characterized by comprising the following steps:
(1) Stirring the resin base material at a rotating speed of 1000-1500r/min, and adding a solvent and an auxiliary agent in the stirring process;
(2) Continuously stirring, adding graphene, pigment and organic polyamine compound, mixing and stirring for 20-40min;
(3) Filtering and discharging the mixed product.
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